Sorption and binary exchange of nitrate, sulfate, and uranium on an anion-exchange resin

Competitive ion-exchange reactions were studied on a strong-base anion-exchange resin to remove NO3- and uranium from a contaminated groundwater containing high levels of NO3- (approximately 140 mM), SO4(2-) (approximately 10 mM), and U(VI) (approximately 0.2 mM). Results indicate that although SO4(2-) carries divalent negative charges, it showed the least selectivity for sorption by the Purolite A-520E resin, which is functionalized with triethylamine exchange sites. Nitrate was the most strongly sorbed. Sorption selectivity followed the order of NO3- > Cl- > SO4(2-) under the experimental conditions. Nitrate competitively sorbed and displaced previously sorbed SO4(2-) in a column flow-through experiment and resulted in a high elution front of SO4(2-) in the effluent. Although the concentration of uranium in groundwater is orders of magnitude lower than that of NO3- or SO4(2-), it was found to be strongly sorbed by the anion-exchange resin. Because the most stable uranium species in oxic and suboxic environments is the UO2(2+) cation, its strong sorption by anion-exchange resins is hypothesized to be the result of the co-ion effect of NO3- by forming anionic UO2(NO3)3- complexes in the resin matrix. These observations point out a potential alternative remediation strategy that uses strong-base anion-exchange resins to remove uranium from this site-specific groundwater, which has a low pH and a relatively high NO3- concentration.     

Geochemical reactions resulting from in situ oxidation of PCE-DNAPL by KMnO4 in a sandy aquifer

Although the potential for KMnO4 to destroy chlorinated ethenes in situ was first recognized more than a decade ago, the geochemical processes that accompany the oxidation have not previously been examined. In this study, aqueous KMnO4 solutions (10-30 g/L) were injected into an unconfined sand aquifer contaminated by the dense non-aqueous-phase liquid (DNAPL) tetrachloroethylene (PCE). The effects of the injections were monitored using depth-specific, multilevel groundwater samplers, and continuous cores. Two distinct geochemical zones evolved within several days after injection. In one zone where DNAPL is present, reactions between KMnO4 and dissolved PCE resulted in the release of abundant chloride and hydrogen ions to the water. Calcite and dolomite dissolved, buffering the pH in the range of 5.8-6.5, releasing Ca, Mg, and CO2 to the pore water. In this zone, the aqueous Ca/Cl concentration ratio is close to 5:12, consistent with the following reaction for the oxidation of PCE in a carbonate-rich aquifer: 3C2Cl4 + 5CaCO3(s) + 4KMnO4 + 2H+ --> 11CO2 + 4MnO2(s) + H2O + 12Cl- + 5Ca2+ + 4K+. In addition to Mg from dolomite dissolution, increases in the concentration of Mg as well as Na may result from exchange with K at cation-exchange sites. In the second zone, where lesser amounts of PCE were present, KMnO4 persisted in the aquifer for more than 14 months, and the porewater pH increased graduallyto between 9 and 10 as a resultof reaction between KMnO4 and H2O. A small increase in SO4 concentrations in the zones invaded by KMnO4 suggests that KMnO4 injections caused oxidation of sulfide minerals. There are important benefits of carbonate mineral buffering during DNAPL remediation by in situ oxidation. In a carbonate-buffered system, Mn(VII) is reduced to Mn(IV) and is immobilized in the groundwater by precipitating as insoluble manganese oxide. Energy-dispersive X-ray spectroscopy analyses of the manganese oxide coatings on aquifer mineral grains have detected the impurities Al, Ca, Cl, Cu, Pb, P, K, Si, S, Ti, U, and Zn indicating that, similar to natural systems, precipitation of manganese oxide is accompanied by coprecipitation of other elements. In addition, the consumption of excess KMnO4 by reaction with reduced minerals such as magnetite will be minimized because the rates of these reactions increase with decreasing pH. Aquifer cores collected after the KMnO4 injections exhibit dark brown to black bands of manganese oxide reaction products in sand layers where DNAPL was originally present. Mineralogical investigations indicate that the manganese oxide coatings are uniformly distributed over the mineral grains. Observations of the coatings using transmission electron microscopy indicate that they are on the order of 1 microm thick, and consequently, the decrease in porosity through the formation of the coatings is negligible.     

Determination of interstitial water chemistry and porosity in consolidated aquifer materials by diffusion equilibrium-exchange

Diffusion equilibrium exchange (DEE) is presented as a novel, practical alternative to centrifugation for the recovery and chemical analysis of interstitial water in contaminated core samples from consolidated rocks and aquifers. The methodology is suitable for sampling organic and inorganic compounds, including redox sensitive species such as SO4(2-), NO3-, NO2-, Mn(II), Fe(II), and sulfide (HS-). DEE also permits analyte extraction from kilogram quantities of core, which avoids extended centrifugation or sample amalgamation and provides analyte masses appropriate for stable isotope analysis. The procedure involves simple and rapid on-site sectioning of representative core samples, which are preserved in the field by storage in airtight bottles filled with deoxygenated deionized water containing a conservative tracer (Br-). Equilibration times for individual solutes can be estimated in advance to reduce the need for time-series analysis; for an effective diffusion coefficient of 2.5 x 10(-10) m2 s(-1) (Br- in chalk rock) equilibration was >90% completed after 30 h, consistent with the predicted equilibration time. The DEE method presented minimizes sampling errors from temperature changes, oxidation of reduced chemical species, and loss of volatile compounds, which can occur with other interstitial water sampling techniques. It also gives superior resolution of in situ solute distributions and geochemical processes in consolidated sediments than centrifugation and can provide estimates of aquifer porosity in core samples. Laboratory experiments using chalk rock core and simulated extraction procedures confirm the superior performance of the DEE method over centrifugation for a range of solutes. The method has been used to generate detailed interstitial water profiles of electron acceptor and contaminant concentrations along the flow path of a petroleum hydrocarbon plume in the U.K. Upper Chalk aquifer as part of a natural attenuation assessment.     

Conversion of fogwater and aerosol organic nitrogen to ammonium,nitrate, and NOx during exposure to simulated sunlight and ozone

Although organic nitrogen (ON) compounds are apparently ubiquitous in the troposphere, very little is known about their fate and transformations. As one step in addressing this issue, we have studied the transformations of bulk (uncharacterized) organic nitrogen in fogwaters and aerosol aqueous extracts during exposure to simulated sunlight and O3. Our results show that over the course of several hours of exposure a significant portion of condensed-phase organic nitrogen is transformed into ammonium, nitrite, nitrate, and NOx. For nitrite, there was both photochemical formation and destruction, resulting in a slow net loss. Ammonium and nitrate were formed at initial rates on the order of a few micromolar per hour in the bulk fogwaters, corresponding to formation rates of approximately 10 and 40 ng m(-3) h(-1), respectively, in ambient fog. The average initial formation rate (expressed as ng (m of air)(-3) h(-1)) of NH4+ in the aqueous extracts of fine particles (PM2.5) was approximately one-half of the corresponding fogwater value. Initial formation rates of NOx (i.e., NO + NO2) were equivalent to approximately 2-11 pptv h(-1) in the three fogwaters tested. Although the formation rates of ammonium and nitrate were relatively small as compared to their initial concentrations in fogwaters (approximately 200-2000 microM) and aerosol particles (approximately 400-1500 ng m(-3)), this photochemical mineralization and "renoxification" from condensed-phase organic N is a previously uncharacterized source of inorganic N in the atmosphere. This conversion also represents a new component in the biogeochemical cycle of nitrogen that might have significant influences on atmospheric composition, condensed-phase properties, and the ecological impacts of N deposition.     

In situ chemical reduction of aquifer sediments: enhancement of reactive iron phases and TCE dechlorination

In situ chemical reduction of aquifer sediments is currently being used for chromate and TCE remediation by forming a permeable reactive barrier. The chemical and physical processes that occur during abiotic reduction of natural sediments during flow by sodium dithionite were investigated. In different aquifer sediments, 10-22% of amorphous and crystalline FeIII-oxides were dissolved/reduced, which produced primarily adsorbed FeII, and some siderite. Sediment oxidation showed predominantly one FeII phase, with a second phase being oxidized more slowly. The sediment reduction rate (3.3 h batch half-life) was chemically controlled (58 kJ mol(-1)), with some additional diffusion control during reduction in sediment columns (8.0 h half-life). It was necessary to maintain neutral to high pH to maintain reduction efficiency and prevent iron mobilization, as reduction generated H+. Sequential extractions on reduced sediment showed that adsorbed ferrous iron controlled TCE reactivity. The mass and rate of field-scale reduction of aquifer sediments were generally predicted with laboratory data using a single reduction reaction.     

Geochemical and geophysical examination of submarine groundwater discharge and associated nutrient loading estimates into Lynch Cove, Hood Canal, WA

Geochemical tracer data (i.e., 222Rn and four naturally occurring Ra isotopes), electromagnetic (EM) seepage meter results, and high-resolution, stationary electrical resistivity images were used to examine the bi-directional (i.e., submarine groundwater discharge and recharge) exchange of a coastal aquifer with seawater. Our study site for these experiments was Lynch Cove, the terminus of Hood Canal, WA, where fjord-like conditions dramatically limit water column circulation that can lead to recurring summer-time hypoxic events. In such a system a precise nutrient budget may be particularly sensitive to groundwater-derived nutrient loading. Shore-perpendicular time-series subsurface resistivity profiles show clear, decimeter-scale tidal modulation of the coastal aquifer in response to large, regional hydraulic gradients, hydrologically transmissive glacial terrain, and large (4-5 m) tidal amplitudes. A 5-day 222Rn time-series shows a strong inverse covariance between 222Rn activities (0.5-29 dpm L(-1)) and water level fluctuations, and provides compelling evidence for tidally modulated exchange of groundwater across the sediment/water interface. Mean Rn-derived submarine groundwater discharge (SGD) rates of 85 +/- 84 cm d(-1) agree closely in the timing and magnitude with EM seepage meter results that showed discharge during low tide and recharge during high tide events. To evaluate the importance of fresh versus saline SGD, Rn-derived SGD rates (as a proxy of total SGD) were compared to excess 226Ra-derived SGD rates (as a proxy for the saline contribution of SGD). The calculated SGD rates, which include a significant (>80%) component of recycled seawater, are used to estimate associated nutrient (NH4+, Si, PO4(3-), NO3 + NO2, TDN) loads to Lynch Cove. The dissolved inorganic nitrogen (DIN = NH4 + NO2 + NO3) SGD loading estimate of 5.9 x 10(4) mol d(-1) is 1-2 orders of magnitude larger than similar estimates derived from atmospheric deposition and surface water runoff, respectively.     

Effects of pH and catalyst concentration on photocatalytic oxidation of aqueous ammonia and nitrite in titanium dioxide suspensions

Batch experiments were conducted to study the effects of titanium dioxide (TiO2) concentration and pH on the initial rates of photocatalytic oxidation of aqueous ammonium/ ammonia (NH4+/NH3) and nitrite (NO2-) in UV-illuminated TiO2 suspensions. While no simple kinetic model could fit the data at lower TiO2 concentrations, at TiO2 concentrations > or = 1 g/L, the experimental data were consistent with a model assuming consecutive first-order transformation of NH4+/NH3 to NO2- and NO2- to nitrate (NO3-). For TiO2 concentrations > or = 1 g/L, the rate constants for NO2 photocatalytic oxidation to NO3 were far more dependent on TiO2 concentration than were those for NH4+/NH3 oxidation to NO2-, suggesting that, without sufficient TiO2, complete oxidation of NH4+/NH3 to NO3- will not occur. Initial NH4+/NH3 photocatalytic oxidation rates were proportional to the initial concentrations of neutral NH3 and not total NH3(i.e., [NH4+] + [NH3]). Thus, the pH-dependent equilibrium between NH4+ and NH3, and not the pH-dependent electrostatic attraction between NH4+ and the TiO2 surface, is responsible for the increase in rates of NH4+/NH3 photocatalytic oxidation with increasing pH. Electrostatic adsorption, however, can partly explain the pH dependence of the initial rates of NO2- photocatalytic oxidation. Initial rates of NO2- photocatalytic oxidation were 1 order of magnitude higher for NO2- versus NH4+/NH3, indicating thatthe rate of NH4+/NH3 photocatalytic oxidation to NO3- was limited by NH4+/NH3 oxidation to NO2- under our experimental conditions.     

Major anion effects on the kinetics and reactivity of granular iron in glass-encased magnet batch reactor experiments

The relative effects of sulfate (SO4(2-)), chloride (Cl-), nitrate (NO3-), and bicarbonate (HCO3-) (8 mM ionic strength solutions, adjusted to pH 10) on the reactivity of Master Builders iron was investigated using a low-abrasion batch reactor with a glass-encased magnet (GEM). Reactivity of the granular iron surface was assessed by measuring the reduction rate of 4-chloronitrobenzene (4ClNB) as a function of initial 4CINB concentration and anion type. Relative to a similarly prepared perchlorate (ClO4-) solution, in which perchlorate was assumed not to interact with the iron surface, nitrate and bicarbonate inhibited the reduction of the probe compound (4ClNB). Chloride and sulfate enhanced reactivity. Thus, the anions were ranked SO4(2-) > Cl- > or = ClO4- > NO3- > HCO3 (from most enhanced to most inhibited) in their influence on granular iron reactivity toward 4ClNB. Kinetic studies of 4CINB were conducted under conditions that caused the iron surface to saturate with the reacting compound (saturation kinetic studies). These experiments, conducted in the various anion solutions indicated above, showed that the gains in reactivity that occurred in the presence of Cl- and SO4(2-) were due to either increased surface reactivity or sorption capacity. The losses in reactivity that occurred in the presence of NO3- were due to decreases in one or both of these same two factors. However, reactivity declines in the presence of CO3(2-) appear to have been due, in large part, to a reduced affinity of 4ClNB for the iron surface.     

Bench-scale investigation of permanganate natural oxidant demand kinetics

A vital design parameter for any in situ chemical oxidation system using permanganate (MnO4-) is the natural oxidant demand (NOD), a concept that represents the consumption of MnO4- by the naturally present reduced species in the aquifer solids. The data suggest that the NOD of the aquifer material from Canadian Forces Base Borden used in our study is controlled by a fast or instantaneous reaction captured by the column experiments, and a slower reaction as demonstrated by both column and batch test data. These two reaction rates may be the result of the reaction of MnO4- with at least two different reduced species exhibiting widely different rates of permanganate consumption (fast rate >7 g of MnO4- as KMnO4/kg/day and slow rate of approximately 0.005 g/kg/day), or a physically/chemically rate-limited single species. The slow NOD reaction prevented fulfillment of the ultimate NOD during the days- to months-long batch experiments and allowed significant early MnO4- breakthrough (>98%) during transport in the column experiments. A large fraction of the organic carbon resisted oxidation over the 21-week duration of the batch experiments. This result demonstrates that NOD estimated from total organic carbon measurements can significantly overpredict the NOD value required in the design of an in situ chemical oxidation application.     

Reduction of nitroglycerin with elemental iron: pathway, kinetics, and mechanisms

Nitroglycerin (NG) is a nitrate ester used in dynamites, propellants, and medicines and is therefore a common constituent in propellant-manufacturing and pharmaceutical wastewaters. In this study we investigated the reduction of NG with cast iron as a potential treatment method. NG was reduced stepwise to glycerol via 1,2- and 1,3-dinitroglycerins (DNGs) and 1- and 2-mononitroglycerins (MNGs). Nitrite was released in each reduction step and was further reduced to NH4+. Adsorption of NG and its reduction products to cast iron was minimal. A reaction pathway and a kinetic model for NG reduction with cast iron were proposed. The estimated surface area-normalized reaction rate constants for NG and NO2- were (1.65 +/- 0.30) x 10(-2) (L x m(-2) x h(-1)) and (0.78 +/- 0.09) x 10(-2) (L x m(-2) x h(-1)), respectively. Experiments using dialysis cell with iron and a graphite sheet showed that reduction of NG to glycerol can be mediated by graphite. However, reduction of NO2- mediated by graphite was very slow. NG and NO2- were also found to reduce to glycerol and NH4+ by Fe2+ in the presence of magnetite but not by aqueous Fe2+ or magnetite alone. These results indicate that in a cast iron-water system NG may be reduced via multiple mechanisms involving different reaction sites, whereas nitrite is reduced mainly by iron and/ or adsorbed Fe2+. The study demonstrates that iron can rapidly reduce NG to innocuous and biodegradable end products and represents a new approach to treat NG-containing wastewaters.     

Novel dry-desulfurization process using Ca(OH)2/fly ash sorbent in a circulating fluidized bed

A dry-desulfurization process using Ca(OH)2/fly ash sorbent and a circulating fluidized bed (CFB) was developed. Its aim was to achieve high SO2 removal efficiency without humidification and production of CaSO4 as the main byproduct. The CaSO4 produced could be used to treat alkalized soil. An 83% SO2 removal rate was demonstrated, and a byproduct with a high CaSO4 content was produced through baghouse ash. These results indicated that this process could remove SO2 in flue gas with a high efficiency under dry conditions and simultaneously produce soil amendment. It was shown that NO and NO2 enhanced the SO2 removal rate markedly and that NO2 increased the amount of CaSO4 in the final product more than NO. These results confirmed that the significant effects of NO and NO2 on the SO2 removal rate were due to chain reactions that occurred under favorable conditions. The amount of baghouse ash produced increased as the reaction progressed, indicating that discharge of unreacted Ca(OH)2 from the reactor was suppressed. Hence, unreacted Ca(OH)2 had a long residence time in the CFB, resulting in a high SO2 removal rate. It was also found that 350 degrees C is the optimum reaction temperature for dry desulfurization in the range tested (320-380 degrees C).     

Influence of agricultural biomass burning on aerosol size distribution and dry deposition in southeastern Brazil

The size distributed composition of ambient aerosols is used to explore seasonal differences in particle chemistry and to show that dry deposition fluxes of soluble species, including important plant nutrients, increase during periods of biomass (sugar cane trash) burning in S?o Paulo State, Brazil. Measurements were made at a single site centrally located in the State's sugar cane growing region but away from the immediate vicinity of burns, so that the airsampled was representative of the regional background. Calculation of ion equivalent balances showed that during burning periods smaller particles (Aitken and accumulation modes) were more acidic, containing higher concentrations of SO4(2-), oxalate, NO3-, HCOO-, CH3COO-, and CI-, but insufficient NH4+ and K+ to achieve neutrality. Larger particles showed an anion deficit due to the presence of unmeasured ions and comprised resuspended dusts modified by accumulation of nitrate, chloride, and organic anions. Increases of resuspended particles during the burning season were attributed to release of earlier deposits from the surfaces of burning vegetation as well as increased vehicle movement on unsurfaced roads. During winter months the relative contribution of combined emissions from road transport and industry diminished due to increased emissions from biomass combustion and other activities specifically associated with the harvest period. Positive increments in annual particulate dry deposition fluxes due to higher fluxes during the sugar cane harvest were 44.3% (NH4+), 42.1% (K+), 31.8% (Mg2+), 30.4% (HCOO-), 12.8% (CI-), 6.6% (CH3COO-), 5.2% (Ca2+), 3.8% (SO4(2-)), and 2.3% (NO3-). Na+ and oxalate fluxes were seasonally invariant. Annual aerosol dry deposition fluxes (kg ha(-1)) were 0.5 (Na+), 0.25 (NH4+), 0.39 (K+), 0.51 (Mg2+), 3.19 (Ca2+), 1.34 (Cl-), 4.47 (NO3-), 3.59 (SO4(2-)), 0.58 (oxalate), 0.71 (HCOO-), and 1.38 (CH3COO-). Contributions of this mechanism to combined aerosol dry deposition and precipitation scavenging (inorganic species, excluding gaseous dry deposition) were 31% (Na+), 8% (NH4+), 26% (K+), 63% (Mg2+), 66% (Ca2+), 32% (Cl-), 33% (NO3-), and 36% (SO4(2-)).     

Field measurements of aerosol particle dry deposition on tropical foliage at an urban site

This paper presents dry deposition of major ions on tropical foliage (leaves of Ashok (Polyalthia longifolia) and Cassia (Cassia siamea)) at St. John's, Agra, an urban site of tropical India on nonrainy, nondewy, and nonfoggy days. The deposition flux was higher on Cassia leaf than Ashok leaf probably due to a rougher surface as shown by scanning electron microscopy. Dry deposition of cations varies from 0.46 to 12.16 mg m(-2) day(-1) while anions vary from 0.04 to 3.24 mg m(-2) day(-1). The percentage contribution of alkaline components is greater than that of acidic components, indicating the alkaline nature of dry deposition. Two-way analysis of variance results reveal significant seasonal variation only for K+, SO4(2-), and F-; however, values varied season to season for Na+, Ca2+, Mg2+, Cl-, NO3-, and NH4+ also. The large seasonal variation in deposition flux may be due to meteorological conditions, diameter of particles, and variation in atmospheric level. SO42- and NO3- show significant correlation, indicating their origin from similar sources while significant correlation between Ca2+ and Mg2+ implies their origin from soil. Poor correlation between Ca2+ and SO4(2-), Ca2+ and NO3-, and Mg2+ and SO4(2-) indicates that in addition to soil other sources also contribute to dry deposition. Low dry deposition fluxes of SO2- and NO3- compared to Ca2+ and Mg2+ may be due to low mass medium diameters of SO4(2-) and NO3- and may be due to uptake through the stomatal pores abundant on leaf surfaces. Factor analysis was employed to identify the sources. F-, Cl, SO4(2-), NO3-, and K+ are grouped together in the first factor, indicating their probable contribution from combustion, Ca2+, Mg2+, and NH4+ are grouped in factor II, which may be attributed to road dust and soil, and factor III includes mainly Na+ and F-, probably contributed from brick-kiln industries. Atmospheric concentrations of F-, Cl-, NOs-, SO4(2-), Na+, K+, Ca2+, Mg2+, and NH4+ were found to be 0.38, 2.28, 1.31, 2.74, 0.44, 0.59, 1.21, 1.2, and 2.29 microg m(-3), respectively.     

Laboratory studies of potential mechanisms of renoxification of tropospheric nitric acid

Laboratory studies of the heterogeneous reactions between HNO3 in thin water films on silica surfaces and gaseous NO, CO, CH4, and SO2, proposed as potential "renoxification" mechanisms in the atmosphere, are reported. Transmission FTIR was used to monitor reactants and products on the silica surface and in the gas phase as a function of time. No reaction of CO, CH4, or SO2 was observed; upper limits to the reaction probabilities (gamma(rxn)) are < or = 10(-10) for CO and SO2 and < or = 10(-12) for CH4. However, the reaction of HNO3 with NO does occur with a lower limit for the reaction probability of gammaNO > or = (6 +/- 2) x 10(-9) (2s). The experimental evidence shows that the chemistry is insensitive to whether the substrate is pure silica or borosilicate glass. Nitric acid in its molecular form, and not the nitrate anion form, was shown to be the reactive species, and NH4NO3 was shown not to react with NO. The HNO3-NO reaction could be a significant means of renoxification of nitric acid on the surfaces of buildings and soils in the boundary layer of polluted urban atmospheres. This chemistry may help to resolve some discrepancies between model-predicted ozone and field observations in polluted urban atmospheres.     

Sources of sulfate supporting anaerobic metabolism in a contaminated aquifer

Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis-Menten-like relationship with an apparent Km and Vmax of approximately 80 and 0.83 microM SO4(-2) x day(-1), respectively. The concentration of sulfate in the core of the leachate plume was well below 20 microM and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (approximately 100 microM) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.     

Effects of the antimicrobial sulfamethoxazole on groundwater bacterial enrichment

The effects of "trace" (environmentally relevant) concentrations of the antimicrobial agent sulfamethoxazole (SMX) on the growth, nitrate reduction activity, and bacterial composition of an enrichment culture prepared with groundwater from a pristine zone of a sandy drinking-water aquifer on Cape Cod, MA, were assessed by laboratory incubations. When the enrichments were grown under heterotrophic denitrifying conditions and exposed to SMX, noticeable differences from the control (no SMX) were observed. Exposure to SMX in concentrations as low as 0.005 μM delayed the initiation of cell growth by up to 1 day and decreased nitrate reduction potential (total amount of nitrate reduced after 19 days) by 47% (p=0.02). Exposure to 1 μM SMX, a concentration below those prescribed for clinical applications but higher than concentrations typically detected in aqueous environments, resulted in additional inhibitions: reduced growth rates (p=5×10(-6)), lower nitrate reduction rate potentials (p=0.01), and decreased overall representation of 16S rRNA gene sequences belonging to the genus Pseudomonas. The reduced abundance of Pseudomonas sequences in the libraries was replaced by sequences representing the genus Variovorax. Results of these growth and nitrate reduction experiments collectively suggest that subtherapeutic concentrations of SMX altered the composition of the enriched nitrate-reducing microcosms and inhibited nitrate reduction capabilities.     

Photocatalytic degradation and mineralization of commercial methamidophos in aqueous titania suspension

The photocatalytic degradation of a commercial methamidophos (MAP) emulsion in aqueous suspension containing mesoporous titania (m-TiO2) nanoparticles under UV irradiation was investigated. The mineralization rate of MAP went up steadily as prolonging the irradiation time and reached ca. 95% after 4 h irradiation based on determination of the end-products (NO3-, PO4(3-), and SO4(2-)) of MAP through IC analysis. Moreover, the degradation kinetics of MAP followed the first-order reaction and has been monitored through GC-PFPD analysis, which also showed that MAP and the organic solvent as well as additive in the pesticide emulsion can be degraded readily and simultaneously. Photodegradation intermediates derived from two different concentrations of MAP were detected by GC-MS technique. The experimental facts indicated that the photodegradation mechanism of MAP mainly involves electron transfer process and hydroxylation process, and the dominant mechanism for MAP degradation in the initial steps can be attributed to the electron transfer process, which resulted in the formation of all intermediates containing P species detected in the initial photodegradation stage.     

Direct nanoscale observations of CO2 sequestration during brucite [Mg(OH)2] dissolution

The dissolution and carbonation of brucite on (001) cleavage surfaces was investigated in a series of in situ and ex situ atomic force microscopy (AFM) experiments at varying pH (2-12), temperature (23-40 °C), aqueous NaHCO(3) concentration (10(-5)-1 M), and PCO(2) (0-1 atm). Dissolution rates increased with decreasing pH and increasing NaHCO(3) concentration. Simultaneously with dissolution of brucite, the growth of a Mg-carbonate phase (probably dypingite) was directly observed. In NaHCO(3) solutions (pH 7.2-9.3,), precipitation of Mg-carbonates was limited. Enhanced precipitation was, however, observed in acidified NaHCO(3) solutions (pH 5, DIC ≈ 25.5 mM) and in solutions that were equilibrated under a CO(2) atmosphere (pH 4, DIC ≈ 25.2 mM). Nucleation predominantly occurred in areas of high dissolution such as deep step edges suggesting that the carbonation reaction is locally diffusion-transport controlled. More extensive particle growth was also observed after ex situ experiments lasting for several hours. This AFM study contributes to an improved understanding of the mechanism of aqueous brucite carbonation at low temperature and pressure conditions and has implications for carbonation reactions in general.     

Solution chemistry effects on orthophosphate adsorption by cationized solid wood residues

Adsorption of orthophosphate anions in aqueous solution by cationized milled solid wood residues was characterized as a function of sorbate-to-sorbent ratio (approximately equal to 0.001-2.58 mmol of P/g substrate), pH (3-9), ionic strength, I (no I control; 0.001 and 0.01 M NaCl), reaction time (4 min to 24 h), and in the presence of other competing anions (0.08-50 mM SO4(2-); 0.08-250 mM NO3-). Sorption isotherms revealed the presence of two kinds of adsorption sites corresponding to high and low binding affinities for orthophosphate anions. Consequently, a two-site Langmuir equation was needed to adequately describe the data over a range of solution conditions. In addition to higher sorption capacity, cationized bark possessed a higher binding energy for orthophosphate anions compared to cationized wood. The sorption capacity and binding energy for bark were 0.47 mmol of P g(-1) and 295.7 L mmol(-1), respectively, and for wood, the corresponding values were 0.27 mmol g(-1) and 61.4 L mmol(-1). Both the sorption capacity and binding energy decreased with increasing I, due to competition from Cl- ions for the available anion-exchange sites. The surface charge characteristics of cationized bark (pHzpc = 7.9) acted in concert with orthophosphate speciation to create a pH-dependent sorption behavior. Orthophosphate uptake was quite rapid and attained equilibrium levels after 3 h. Both SO4(2-) and NO3- influenced percent removal but required high relative competing anion to H2PO4- molar ratios, i.e., 2.5-3 for SO4(2-) and 25 for NO3-, to cause appreciable reduction. These results support our hypothesis that adsorption of orthophosphate anions on cationized bark involves ion exchange and other specific Lewis acid-base interactions.     

Atmospheric chemistry of N-methyl perfluorobutane sulfonamidoethanol, C4F9SO2N(CH3)CH2CH2OH: kinetics and mechanism of reaction with OH

Relative rate methods were used to measure the gas-phase reaction of N-methyl perfluorobutane sulfonamidoethanol (NMeFBSE) with OH radicals, giving k(OH + NMeFBSE) = (5.8 +/- 0.8) x 10(-12) cm3 molecule(-1) s(-1) in 750 Torr of air diluent at 296 K. The atmospheric lifetime of NMeFBSE is determined by reaction with OH radicals and is approximately 2 days. Degradation products were identified by in situ FTIR spectroscopy and offline GC-MS and LC-MS/MS analysis. The primary carbonyl product C4F9SO2N(CH3)CH2CHO, N-methyl perfluorobutane sulfonamide (C4F9SO2NH(CH3)), perfluorobutanoic acid (C3F7C(O)OH), perfluoropropanoic acid (C2F5C(O)OH), trifluoroacetic acid (CF3C(O)OH), carbonyl fluoride (COF2), and perfluorobutane sulfonic acid (C4F9SO3H) were identified as products. A mechanism involving the addition of OH to the sulfone double bond was proposed to explain the production of perfluorobutane sulfonic acid and perfluorinated carboxylic acids in yields of 1 and 10%, respectively. The gas-phase N-dealkylation product, N-methyl perfluorobutane sulfonamide (NMeFBSA), has an atmospheric lifetime (>20 days) which is much longer than that of the parent compound, NMeFBSE. Accordingly,the production of NMeFBSA exposes a mechanism by which NMeFBSE may contribute to the burden of perfluorinated contamination in remote locations despite its relatively short atmospheric lifetime. Using the atmospheric fate of NMeFBSE as a guide, it appears that anthropogenic production of N-methyl perfluorooctane sulfonamidoethanol (NMeFOSE) contributes to the ubiquity of perfluoroalkyl sulfonate and carboxylate compounds in the environment.