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Validation of an arsenic sequential extraction method for evaluating mobility in sediments.

Arsenic (As) mobility and transport in the environment are strongly influenced by arsenic's associations with solid phases in soil and sediment. We have tested a sequential extraction procedure intended to differentiate the following pools of solid phase arsenic: loosely and strongly adsorbed As; As coprecipitated with metal oxides or amorphous monosulfides; As coprecipitated with crystalline iron (oxyhydr)oxides; As oxides; As coprecipitated with pyrite; and As sulfides. Additions of As-bearing phases to wetland and riverbed sediment subsamples were quantitatively recovered by the following extractants of the sequential extraction procedure: As adsorbed on goethite, 1 M NaH2PO4; arsenic trioxide (As2O3), 10 M HF; arsenopyrite (FeAsS), 16 N HNO3; amorphous As sulfide, 1 N HCI, 50 mM Ti-citrate-EDTA, and 16 N HNO3; and orpiment (As2S3), hot concentrated HNO3/H2O2. Wet sediment subsamples from both highly contaminated wetland peat and less As-rich sandy riverbed sediment were used to test the extraction procedure for intra-method reproducibility. The proportional distribution of As among extractant pools was consistent for subsamples of the wetland and for subsamples of the riverbed sediments. In addition, intermethod variability between the sequential extraction procedure and a single-step hot concentrated HNO3/H2O2 acid digestion was investigated. The sum of the As recovered in the different extractant pools was not significantly different than results for the acid digestion.

Arsenic↗

Phytochelatins are bioindicators of atmospheric metal exposure via direct foliar uptake in trees near Sudbury, Ontario, Canada.

Plants produce phytochelatins in response to copper and nickel, the primary metal pollutants emitted by the dominant smelting operation in Sudbury. Copper and nickel concentrations in soils decline sharply with distance from this facility, primarily as a result of early smelting practices. Phytochelatin concentrations in Sudbury-area trees, however, do not correlate with metal levels in soils. Rather, phytochelatin production in tree leaves is driven by metals currently released to the atmosphere through the 381 m emissions stack. Phytochelatin concentrations in the foliage of three tree species growing in situ are highest 20-30 km from the stack, correlated with maximum acid-leachable concentrations of deposited copper and nickel. Similar results observed in potted trees placed adjacent to indigenous trees confirm that aerially deposited metals are the source of current metal stress patterns. The addition of peat moss "filters" to potted soils did not alter this response, indicating that direct foliar metal uptake is responsible.

Air Pollutants↗

Quantification and prediction of the detoxifying properties of humic substances related to their chemical binding to polycyclic aromatic hydrocarbons.

Effects of 27 different humic materials on the toxicity of polycyclic aromatic hydrocarbons (PAH) were studied for crustacean Daphnia magna. Sources included isolated humic acids, fulvic acids, and their combination from soil, peat, and freshwater. The PAH used were pyrene, fluoranthene, and anthracene. The observed reduction in toxicity of PAH in the presence of humic substances (HS) was shown to be a result of the detoxification effect caused by the chemical binding of PAH to HS and of the direct effect of HS on D. magna. An approach was developed to quantify the detoxifying impact of humic materials related to their chemical binding to PAH with a use of the "constant of detoxification" or "toxicological partition coefficient" K(oc)D. The latter was proposed to determine by fitting the experimental relationships of the detoxification effect versus concentration of HS. The obtained K(oc)D values were well tracked by the corresponding partition coefficients determined by the fluorescence quenching technique (K(oc)fq): K(oc)D=b x K(oc)fq, b (mean+/-Cl, n=26, P=95%)=2.6+/-0.3, 4.6+/-0.6, and 6.0+/-1.4 for pyrene, fluoranthene, and anthracene, respectively. The predictive relationships between the structure and detoxifying properties of humic materials in relation to PAH were developed. It was shown that the magnitude of the K(oc)D values correlated closely with the aromaticity of humic materials characterized with the 13C NMR descriptors (sigma(C)Ar, sigma(C)Ar/sigma(C)Alk) and atomic H/C ratio. The obtained relationships showed the highest detoxifying potential of the humic materials enriched with aromatics and allowed a conclusion on the chemical binding as the governing mechanism of the mitigating action of HS on the toxicity of PAH.

Animals↗

Fluorescence excitation-emission matrix characterization of river waters impacted by a tissue mill effluent.

Fluorescence excitation-emission matrix (EEM) spectrophotometry was applied to five neighboring rivers, including one that is impacted by wastewater from a large tissue mill, to determine if fluorescence spectrophotometry could be used to differentiate between the river waters. River water samples from both the tissue mill effluent and the impacted river, the Park Burn, exhibited significantly higher fluorescence intensity than the other sites. This fluorescence was dominated by tryptophan fluorescence and a fluorescence center possibly due to the presence of fluorescent whitening agents. In contrast, the three other rivers exhibited lower fluorescence intensities typical of river systems with tryptophan (sewage), humic-like (peat derived color), and fulvic-like (natural organic matter) sources. It is suggested that fluorescence EEM spectrophotometry has the potential to provide a useful tool for pollution detection, monitoring, and control of paper industry impacts on river systems.

Benzopyrans↗

Historical trends in the lead isotopic composition of archival Sphagnum mosses from Scotland (1838-2000).

The analysis of almost 200 Scottish Sphagnum moss samples collected over the past 170 years has revealed trends in the isotopic composition of lead similar to those previously established for dated Scottish lake sediments and peat bogs, lending credibility to these proxy records of atmospheric lead contamination and deposition. The effect of temporal variations in contributions from sources such as smelting of indigenous lead ores (206Pb/207Pb approximately 1.16-1.18), coal combustion (206Pb/207Pb approximately 1.17-1.19), and the use of imported Australian lead (206Pb/207Pb approximately 1.04) was clearly seen in the Scottish moss 206Pb/207Pb record. This showed some differences from the corresponding archival herbage record for the south of England, where the initial influence of Australian lead occurred earlier, at the end of the 19th century. A significant decline from a 206Pb/ 207Pb value of approximately 1.17 in the Scottish moss record began in the 1920s and continued until the 1980s (206Pb/207Pb approximately 1.12). The success of measures to reduce lead emissions to the atmosphere over the past 20 years in the U.K., in particular from petrol-engined vehicles using alkyl lead additives manufactured primarily from Australian lead, is evident in both the increasing 206Pb/207Pb ratio and falling lead concentration data for Scottish moss.

Bryopsida↗

Correlation of poly(methylene)-rich amorphous aliphatic domains in humic substances with sorption of a nonpolar organic contaminant phenanthrene.

The structural makeup of natural organic matter plays a major role in regulating its capacity to retain nonionic hydrophobic organic compounds (HOCs). We used a model HOC--phenanthrene--to investigate the correlations between sorption capacity, specifically the modified Freundlich coefficient (K'f), and compositional data of humic acids, humins, and a peat obtained from quantitative 13C solid-state NMR spectroscopy. A positive correlation between K'f and the weight fraction of amorphous poly(methylene) in the sorbents was observed. In contrast, the correlation between phenanthrene sorption capacity and aromaticity or polarity indices of the sorbents was insignificant. The nonpolar aliphatic carbon fraction, excluding poly(methylene), was only partially correlated with K'f. Detailed NMR analyses of the sorbents using 1H inversion-recovery experiments showed that 10-nm diameter domains of branched nonpolar aliphatic groups, which account for 20-50% of all nonpolar aliphatic segments and may be associated with the poly(methylene), were responsible for the partial correlation. The correlation between K'f and the amorphous nonpolar aliphatic domains including amorphous poly(methylene) was strong. The rubbery, relatively low-density, and amorphous nonpolar aliphatic domains can be expected to offer an excellent environment for the sorption of phenanthrene by partitioning. These observations suggest that the domains of amorphous poly(methylene) and branched nonpolar aliphatics, which make up 2-9 wt % of the organic fraction in our samples, may serve as good descriptors for the potential of natural organic matter to retain HOCs in the natural environments.

Adsorption↗

Induced phytoextraction/soil washing of lead using biodegradable chelate and permeable barriers.

Chelate-induced remediation has been proposed as an effective tool for the extraction of lead (Pb) from contaminated soils by plants. However, side-effects, mainly mobilization and leaching of Pb, raise environmental concerns. Biodegradable, synthetic organic chelate ethylenediaminedisuccinic acid (EDDS), and commonly used ethylenedimanetetraacetic acid (EDTA) were used for induced phytoextraction with a test plant Brassica rapa and in situ washing of soil contaminated with 1350 mg/kg of Pb. Horizontal permeable barriers were placed 20 cm deep in soil columns and tested for their ability to prevent leaching of Pb. The reactive materials in the barriers were nutrient enriched vermiculite, peat or agricultural hydrogel, and apatite. EDTA and EDDS addition increased Pb concentrations in the test plant by 158 and 89 times compared to the control, to 817 and 464 mg/kg, respectively. In EDTA treatments, approximately 25% or more of total initial soil Pb was leached in single cycle of chelate addition. In EDDS treatments, 20% of the initial Pb was leached from columns with no barrier, while barriers with vermiculite or hydrogel and apatite decreased leaching by more than 60 times, to 0.35%. 11.6% of total initial Pb was washed from the soil above the barrier with vermiculite and apatite, where almost all leached Pb was accumulated. Results indicate that use of biodegradable chelate EDDS and permeable barriers may lead to environmentally safe induced Pb phytoextraction and in situ washing of Pb.

Aluminum Silicates↗

Relationship between strength of organic sorbate interactions in NOM and hydration effect on sorption.

According to a recent conceptual model for hydration-assisted sorption of organic compounds in natural organic matter (NOM), certain polar moieties of dry NOM are unavailable for compound sorption due to strong intra- and intermolecular NOM interactions. Water molecules solvate these moieties creating new sorption sites at solvated contacts. It is expected that the greater a compound's ability to undergo specific interactions with NOM, the greater will be the hydration-assisted sorption effect, because penetration of compounds into solvated contacts must involve competition with water at the solvated contact. To test this model, we compare the hydration effect on sorption kinetics and equilibrium for 4 compounds with differing abilities to undergo specific interactions with NOM. Sorption measured on Pahokee peat in aqueous systems was fast compared with n-hexadecane (dry) systems. No concentration effect on attainment of sorption equilibrium was observed. m-Nitrophenol exhibited the greatest hydration-assisted sorption effect, benzyl alcohol showed an intermediate effect and acetophenone and nitrobenzene showed no hydration-assisted sorption, on an activity scale. The extent of hydration-assisted sorption effect correlates with compound ability to undergo specific interactions. These results support the conceptual model and demonstrate the importance of polar NOM noncovalent links in organizing the NOM phase and in controlling the hydration effect on sorption of organic compounds.

Adsorption↗

Diffusion coefficients of humic substances in agarose gel and in water.

Measurements of the diffusion coefficients of five different humic substances (HS) have been performed in water and in agarose hydrogels at several pH values (in the range of 3-10) and gel concentrations (in the range of 0.7-3% w/w). Fluorescence correlation spectroscopy (FCS) and classical diffusion cells were used in parallel to probe diffusion over both microscopic and mesoscopic distance scales. In general, agreement between the techniques was reasonable, which indicated that local nonhomogenities in the gel did not play an important role. Diffusion coefficients (D) in the gel were generally in the range of 0.9-2.5 x 10(-10) m2 s(-1) but were generally only 10-20% lower than in solution. At low pH values, one of the studied humic substances (a peat humic acid, PPHA) formed large aggregates that could not penetrate into the gel and therefore could not be defined by a single D value. The observed decreases of D in the gel for other HS were too large to be explained by the tortuousity and obstructive effects of the gel alone. D decreased slightly with increasing gel concentration and increased slightly with pH. Because modifications of D due to pH were similar in both the gel and the free solution, it is unlikely that complexation with the gel was greatly influenced by the pH. Rather, the main effect that appeared to decrease the diffusive flux in gels was likely small increases in the hydrodynamic radii of the humic macromolecules. An anomalous diffusion model was used to describe the FCS data in the gel. The characteristic exponent determined by fitting the autocorrelation functions with this model decreased only slightly (from 0.96 to 0.90) with increasing gel concentration providing support that HS complexation with the gel fibers was not very important. The results have important implications for our understanding of the fate and behavior of the HS and their associated pollutants and for interpreting metal speciation data obtained using gel-covered analytical sensors.

Diffusion↗

Effect of drying on biofilter performance: modeling and experimental approach.

The moisture content of biofilter media is a key parameter for its adequate performance. Control of moisture requires a better understanding of the drying of the support due to changes in inlet air temperature and relative humidity and from metabolic heat production by pollutant oxidation. A dynamic one-dimensional model was developed to describe drying and its effect on biofilter performance. Mass and energy balances were established on an elementary representative volume. The biological reaction term incorporated temperature, water content, and pollutant concentration effects. The model describes the variations in pollutant concentration, air relative humidity, temperature, and water content of the media. It predicts (1) water evaporation from the packing material as a consequence of metabolic heat generation and variations of the relative humidity of the inlet air stream, and (2) the resulting decrease in biofilter performance. The model was validated with biofiltration experiments treating gaseous toluene using peat as support. Various ranges of inlet air relative humidity, temperature, air velocity, and inlet pollutant concentration were assayed.

Air Pollutants↗

Identification and characterization of sorption domains in soil organic matter using strucuturally modified humic acids.

The sorption of phenanthrene was examined in humic acids (HAs) from different sources: a compost, a peat soil, and a mineral soil. Sub-samples of each HA were subjected to bleaching or hydrolysis to remove predetermined chemical groups from their structures. Bleaching successfully removed a large percentage of rigid, aromatic moieties, whereas hydrolysis removed the mobile, carbohydrate components. Phenanthrene sorption by all HAs was nonlinear (N < 1). However, the phenanthrene isotherms of the bleached HAs were more linear than those of the untreated HAs, whereas the removal of the carbohydrate components by hydrolysis produced more nonlinear isotherms. The introduction of pyrene to the phenanthrene sorption system yielded more linear isotherms for all the HAs, indicative of competitive sorption. Proton spin-spin (1H T2) relaxation determined by nuclear magnetic resonance (NMR) was used to identify separate rigid (condensed) and flexible (expanded) 1H populations and to determine their distribution. These 1H domains were highly sensitive to temperature and correlated well with reported glass transition temperatures for HAs. In combination with the chemical treatments, sorption, and spectroscopic data, we were able to observe some significant relationships among chemical groups, sorption behavior, and structural characteristics.

Adsorption↗

Trichloroethylene degradation in a coupled anaerobic/aerobic reactor oxygenated using hydrogen peroxide.

In this work, trichloroethylene (TCE) degradation under combined anaerobic-aerobic conditions was studied in an ethanol-fed biofilm reactor oxygenated using hydrogen peroxide. The reactor was inoculated with a biomass originating from an anaerobic digestor. Granulated peat was added to the reactor as a substratum for biofilm development. Extensive characterization of reactor populations using activity tests and PCR analysis revealed the development of a mutualistic consortium, particularly methanotrophic and methanogenic microorganisms. This consortium was shown to degrade TCE by a combination of reductive and oxidative pathways. A near complete degradation of TCE at a load of 18 mg L(R)(-1) day(-1) was evidenced by a stoichiometric release of inorganic chloride.

Bacteria, Aerobic↗

Classifying NOM-organic sorbate interactions using compound transfer from an inert solvent to the hydrated sorbent.

Interactions of a wide set of organic compounds with model natural organic matter (NOM, Pahokee peat) were examined using a new approach that converts aqueous sorption to compound transfer from n-hexadecane to the hydrated NOM. This conversion accounts for solute-water interactions and applies the same inert reference medium for all compounds of interest, making it possible to classify sorbates according to the strength of sorbate-NOM interactions. Differences in strength of organic compound interactions in the sorbed phase as great as 4-5 orders of magnitude are demonstrated. The strongest interactions were observed for compounds with well-established H-bonding potentials. Considering hydrocarbons and Cl-substituted hydrocarbons, aliphatic compounds gain more upon distribution from the n-hexadecane medium to NOM than do aromatic compounds. Sorption nonlinearity was tested by comparing the change in n-hexadecane-hydrated NOM distribution coefficient (K(d,i)) versus sorbed concentration for the different compounds. Only those compounds that interact most strongly with NOM demonstrated significant sorption nonlinearity, expressed by a strong reduction in K(d,i) as a function of sorbed concentration. The relationship between compound ability to interact with NOM and reduction in K(d,i) as a function of sorbed concentration can be used to characterize compound distribution among different sorption domains.

Adsorption↗

Accurate quantification of aromaticity and nonprotonated aromatic carbon fraction in natural organic matter by 13C solid-state nuclear magnetic resonance.

An improved approach for accurately determining the aromatic carbon fraction (fa) and nonprotonated aromatic carbon fraction (faN) in natural organic matter by solid-state 13C NMR is described. Quantitative peak areas are obtained from direct polarization 13C nuclear magnetic resonance (NMR) under high-speed magic angle spinning (MAS). The problem of overlap between aromatic and alkyl carbon resonances around 90-120 ppm in 13C NMR spectra is solved by a 13C chemical shift anisotropy (CSA) filter technique. After correction for residual spinning sidebands, an accurate value of the aromaticity fa is obtained. To obtain a quantitative faN fraction, dipolar dephasing was adapted for high-speed MAS 13C NMR; the separation of the signals of nonprotonated alkyl and aromatic carbons was achieved by CSA filtering plus dipolar dephasing. The method is demonstrated on a peat humic acid, yielding fa = 45 +/- 2% and faN = (0.64 +/- 0.07) x 45%.

Carbon↗

Sorption-controlled degradation kinetics of MCPA in soil.

The relationship between sorption strength and degradation kinetics has been studied for the pesticide MCPA in a sandy top- and subsoil. After adding two types of sorbents (crushed peat and activated carbon) in various amounts to the sandy soils, sorption, desorption, and mineralization of 14C-MCPA were measured. The obtained Freundlich constants (KF) varied between 0.7 and 27.2 mg(1-nF) x L(nF)/kg, and the first-order mineralization rate constants varied between 0.001 and 0.128 d(-1). The results showed an inverse relationship between sorption strength and mineralization. A higher KF value corresponded to a smaller mineralization rate and less mineralization. A correlation coefficient of r2 = 0.934 between the log-transformed Freundlich desorption coefficient (K(F,des)) and the log-transformed mineralization rate constant (k) was obtained. After 7, 14, 22, and 35 days of incubation, soil samples were consecutively extracted by water, methanol, and 5 M NaOH to separate the remaining 14C into 3 different pools. The extractions showed that the mineralization only proceeded from the water extractable pool of MCPA. Thin-layer chromatography revealed a formation of small amounts of metabolites; <7% of initially added 14C was present as other compounds than 14C-MCPA in the water and methanol extractable pools. The study showed mineralization to be strongly correlated with sorption, represented by the desorption coefficient, and hence stresses the significance of bonding strength for estimating pesticide degradation in soil.

2-Methyl-4-chlorophenoxyacetic Acid↗

Identification of copper binding sites in soil organic matter through chemical modifications and 13C CP-MAS NMR spectroscopy.

Metal binding to an organic peat soil was probed by paramagnetic doping with copper, chemical modifications of the organic matter in the soil, and 13C CP-MAS NMR spin lattice relaxation rate measurements. Carboxyl and hydroxyl functional groups were determined to be most significant in copper uptake by the unmodified soil. Esterification and acetylation of the soil showed that metal binding by carbohydrate structures occurs independently of other functional groups and may even induce a pseudochelation phenomenon. Sorption isotherms corroborate the importance of carbohydrate structures in metal binding. These results suggest that environmental modeling of metal binding and retention in soils should incorporate estimates of the distributions of all functional groups in the soil organic matter (e.g. aliphatic, carbohydrate, phenolic, carboxyl) and their relative binding strengths.

Adsorption↗

Humic substances are soft and permeable: evidence from their electrophoretic mobilities.

Due to the complexity of the humic substances (HS), mathematical models have often been employed to understand their roles in the environment. Since no consensus exists with respect to the structure and conformation of the HS, models have alternatively given them properties corresponding to impermeable hard spheres or fully permeable polyelectrolytes. In this study, the hydrodynamic permeability of standard HS (Suwannee River fulvic, humic, and peat humic acids) are evaluated as a function of pH and ionic strength. A detailed theoretical model is used to determine the softness parameter (lambda0), which characterizes the degree of flow penetration into the HS on the basis of measured values of electrophoretic mobilities, diffusion coefficients, and electric charge densities. Their motion in an electric field is evaluated by a rigorous numerical evaluation of the governing electrokinetic equations for soft particles. The hydrodynamic impact of the polyelectrolyte chains is accounted for by a distribution of Stokes resistance centers and partial dissociation of the hydrodynamically immobile ionogenic groups distributed throughout the polyelectrolyte. The results demonstrate thatthe studied HS are small (radius ca. 1 nm), highly charged (500-650 C g(-1) when all sites are dissociated), and very permeable (typical flow penetration length of 25-50% of the radius, depending on pH). The HS also coagulate slightly when lowering the pH of the solution. Modeling of the HS as hard spheres with a charge and slip plane located at the surface is thus physically inappropriate, as are a number of analytical theories for soft particles that hold for low to moderate electrostatic potentials and large colloids. The shortcomings of these simpler approaches, when interpreting the electrophoretic mobilities of HS, are highlighted by comparison with rigorous theoretical predictions.

Colloids↗

Conditioning-annealing studies of natural organic matter solids linking irreversible sorption to irreversible structural expansion.

The assumption of reversibility underpins the sorption term in current models dealing with the fate and impact of organic compounds in the environment, yet experimentally sorption of organic compounds in soils and sediments often shows "irreversible" behaviors such as hysteresis and the conditioning effect (enhanced repeat sorption). The objective of this study was to test whether a glassy polymer irreversibility model applies to natural organic matter (NOM) solids. Irreversible sorption in polymers is believed to be caused by irreversible expansion and creation of internal micropores by penetrating molecules, leading to enhanced affinity during desorption or subsequent resorption. Using chlorobenzene as a conditioning agent and polychlorinated benzenes as test compounds in a second sorption step, we observed conditioning effects for a peat soil, a soil humic acid, and a model glassy polymer, poly- (vinyl chloride), but not for a model rubbery polymer, poly- (ethylene). The conditioning effect for the two natural solids, probed bythe enhancement in the sorption distribution coefficient of 1,2,4-trichlorobenzene, relaxed upon sample annealing between 45 and 91 degrees C in a manner similar to the relaxation of free volume and enthalpy of glassy polymers. Relaxation of the conditioning effect in the NOM solids depended on annealing temperature and, at a given temperature, followed a double additive exponential rate law with a nonzero constant term descriptive of the final state that depends inversely on temperature. At environmentally relevant temperatures, the conditioning effect may "never" completely relax. The results provide compelling evidence for the glassy, nonequilibrium nature of natural organic matter solids and for irreversible structural expansion as a cause of irreversible sorption.

Adsorption↗