Importance of dissolved neutral mercury sulfides for methyl mercury production in contaminated sediments

Biotic transformation of inorganic mercury, Hg(II), to mono methyl mercury (MeHg) is proposed to be largely controlled by passive uptake of neutral Hg complexes by sulfate reducing bacteria (SRB). In this study, the chemical speciation of Hg(II) in seven locally contaminated sediments covering environments such as (i) brackish water, (ii) low-productivity freshwater, and, (iii) high-productivity freshwater was related to potential Hg methylation rates, determined by incubation at 23 degrees C for 48 h under N2(g), and to total MeHg concentrations in sediments. Pore water speciation was modeled considering Hg complexes with halides, organic thiols [Hg(SR)2(aq), associated to dissolved organic matter], monosulfides, and bisulfides. The sum of neutral mercury sulfides [Hg(SH)20(aq)] and [HgS0(aq)] was significantly, positively (p < 0.001, n = 20) correlated to the specific methylation rate constant (Km, day(-1)) at depths of 5-100 cm in two brackish water sediments. Total Hg, total mercury sulfides or Hg(SR)2(aq) in pore water gave no significant relationships with Km. In two subsets of freshwater sediments, neutral mercury sulfides were positively correlated to total Hg in pore water, and therefore, total Hg also gave significant relationships with Km. The sum of [Hg(SH)20(aq)] and [HgS0(aq)] was significantly, positively correlated to total sediment MeHg (microg kg-1) in brackish waters (p < 0.001, n = 23), in southern, high-productivity freshwaters (p < 0.001, n = 20), as well as in northern, low-productivity freshwater (p = 0.048, n = 6). The slopes (b, b') of the relationships Km (day-1) = a + b([Hg(SH)20(aq)] + [HgS0(aq)]) and MeHg (microg kg-1) = a' + b'([Hg(SH)20(aq)] + [HgS0(aq)]) showed an inverse relationship with the C/N ratio, supposedly reflecting differences in primary production and energy-rich organic matter availability among sites. We conclude that concentrations of neutral inorganic mercury sulfide species, together with the availability of energy-rich organic matter, largely control Hg methylation rates in contaminated sediments. Furthermore, Hg(SH)20(aq) is suggested to be the dominant species taken up by MeHg producing bacteria in organic-rich sediments without formation of HgS(s).     

Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: influence of temperature

The sorption of yttrium and the rare earth elements (YREEs) by amorphous ferric hydroxide was investigated between 10 and 40 degrees C over a range of pH (4.7-7.1) in the absence of solution complexation. Distribution coefficients, defined as iKFe = [MSi]T/([M]T[Fe3+]s), where [MSi]T is the concentration of sorbed YREEs, [M]T is the total dissolved YREE concentration, and [Fe3+]s is the concentration of precipitated iron, increased with increasing temperature over the entire investigated pH range. The observed increase in iKFe was largest for the heavy REEs, indicating that relative log iKFe values (i.e., YREE patterns) vary somewhat with temperature. The pH dependence of YREE sorption was described by a surface complexation model of the form iKFe = (sbeta1[H+](-1) + sbeta2[H+](-2))/(sK1[H+] + 1), where sbetan are stability constants for sorption of free YREE ions (M3+) and sK1 is a surface protonation constant for amorphous ferric hydroxide. The influence of temperature on the YREE surface stability constants (sbeta1 and sbeta2) was characterized by calculating molar enthalpies for M3+ sorption (deltaH1(0) and deltaH2(0)) using the van 't Hoff equation. The deltaH1(0) values appropriate to sbeta1 range from 11.8 to 13.4 kcal/mol, whereas the deltaH2(0) values appropriate to sbeta2 range between 7.7 and 12.3 kcal/mol. These values are on the same order of magnitude as enthalpies of the first hydrolysis step for a variety of cations.     

Effect of aqueous Fe(II) on arsenate sorption on goethite and hematite

Biogeochemical iron cycling often generates systems where aqueous Fe(II) and solid Fe(III) oxides coexist. Reactions between these species result in iron oxide surface and phase transformations, iron isotope fractionation, and redox transformations of many contaminant species. Fe(II)-induced recrystallization of goethite and hematite has recently been shown to cause the repartitioning of Ni(II) at the mineral-water interface, with adsorbed Ni incorporating into the iron oxide structure and preincorporated Ni released back into aqueous solution. However, the effect of Fe(II) on the fate and speciation of redox inactive species incompatible with iron oxide structures is unclear. Arsenate sorption to hematite and goethite in the presence of aqueous Fe(II) was studied to determine whether Fe(II) causes substantial changes in the sorption mechanisms of such incompatible species. Sorption isotherms reveal that Fe(II) minimally alters macroscopic arsenate sorption behavior except at circumneutral pH in the presence of elevated concentrations (10?3 M) of Fe(II) and at high arsenate loadings, where a clear signature of precipitation is observed. Powder X-ray diffraction demonstrates that the ferrous arsenate mineral symplesite precipitates under such conditions. Extended X-ray absorption fine structure spectroscopy shows that outside this precipitation regime arsenate surface complexation mechanisms are unaffected by Fe(II). In addition, arsenate was found to suppress Fe(II) sorption through competitive adsorption processes before the onset of symplesite precipitation. This study demonstrates that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe(II)-iron oxide reactions via competitive adsorption.     

Abiotic reductive dechlorination of cis-dichloroethylene by Fe species formed during iron- or sulfate-reduction

This study investigated reductive dechlorination of cis-dichloroethylene (cis-DCE) by the reduced Fe phases obtained from in situ precipitation, which involved mixing of Fe(II), Fe(III), and S(-II) solutions. A range of redox conditions were simulated by varying the ratio of initial Fe(II) concentration ([Fe(II)](o)) to initial Fe(III) concentration ([Fe(III)](o)) for iron-reducing conditions (IRC) and the ratio of [Fe(II)](o) to initial sulfide concentration ([S(-II)](o)) for sulfate-reducing conditions (SRC). Significant dechlorination of cis-DCE occurred under highly reducing IRC and iron-rich SRC, suggesting that Fe (oxyhydr)oxides including green rusts are highly reactive with cis-DCE but that Fe sulfide as mackinawite (FeS) is nonreactive. Relative concentrations of sulfate to chloride were also varied to examine the anion impact on cis-DCE dechlorination. Generally, slower dechlorination occurred in the batches with higher sulfate concentrations. As indicated by higher dissolved Fe concentration, the slower dechlorination in the presence of sulfate was probably due to the decreased surface-complexed Fe(II). This study demonstrates that the chemical form of reduced Fe(II) is critical in determining the fate of cis-DCE under anoxic conditions.     

Reduction of aqueous chromate by Fe(II)/Fe(III) carbonate green rust: kinetic and mechanistic studies

This work describes the heterogeneous reaction between FeII in carbonate green rust and aqueous chromate, in NaHCO3 solutions at 25 degrees C, and at pH values of 9.3-9.6. Evidence for reduction of CrVI to CrIII and concomitant solid-state oxidation of lattice FeII to FeIII was found from FeII titration and from structural analysis of the solids using FTIR, XRD, SEM, and XPS methods. Results indicate the formation of ferric oxyhydroxycarbonate and the concomitant precipitation of CrIII monolayers at the surface of the iron compound that induce passivation effects and progressive rate limitations. The number of CrIII monolayers formed at the completion of the reaction depends on [FeII]t=0, the molar concentration of FeII(solid) at t=0; on [n(o)]t=0, the molar concentration of reaction sites present at the surface of the solid phase at t=0; and on [CrVI]t=0, the molar concentration of CrVI at t=0. Kinetic data were modeled using a model based on the formation of successive CrIII monolayers, -(d[CrVI]/dt) = sigma(1)j k(i)[S] [CrVI]([n(i - 1)] - [n(i)]) with k(i)[S] (in s(-1) L mol(-1)), the rate coefficient of formation of CrIII monolayer i, and [n(i)] and [n(i - 1)], the molar concentration of CrIII precipitated in monolayer i and monolayer i - 1, respectively. Good matching curves were obtained with kinetic coefficients: k(1)[S] = 5-8 x 10(-4), k(2)[S] = 0.5-3 x 10(-5), and k(3)[S] about 1.7 x 10(-6) s(-1) m(-2) L. The CrVI removal efficiency progressively decreases along with the accumulation of CrIII monolayers at the surface of carbonate green rust particles. In the case of thick green rust particles resulting from the corrosion of iron in permeable reactive barriers, the quantity of FeII readily accessible for efficient CrVI removal should be rather low.     

Impact of transition metals on reductive dechlorination rate of hexachloroethane by mackinawite

Mackinawite, an iron monosulfide, has been shown to be a potential reductant for chlorinated organic compounds under anaerobic conditions. Chlorinated organic compounds are often found with inorganic contaminants. This study investigates the impact of various transition metals on the reductive dechlorination by mackinawite using a readily degradable chlorinated organic compound, hexachloroethane (HCA). Different classes of transition metals show distinct patterns in their impact on the HCA dechlorination: 10(-3) M Cr(III) and Mn(II) (hard metals) decreased the dechlorination rates, while 10(-4), 10(-3), and 10(-2) M Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II) (intermediate/soft metals) increased the rates. The tested hard metals, due to their weak affinity for sulfides, are thought to form surface precipitates of hydroxides around FeS under the experimental conditions with these hydroxides hindering the electron transfer between FeS and HCA. Due to their high affinity for sulfides, however, the tested intermediate/soft metals can react with FeS in various ways: precipitation of pure metal sulfides (MS), formation of metal-substituted FeS by lattice exchange, and coprecipitation of the mixed sulfides in a Fe-M-S system. Fe(II), released as a result of the interaction of FeS with intermediate/soft metals, enhances the HCA dechlorination at the doses of 10(-4) and 10(-3) M through sorbed or dissolved Fe(II) species, while Fe(OH)2(s) formed at the higher dose of 10(-2) M also enhances the reductive dechlorination. Rate increases observed in Co(II)-, Ni(II)-, and Hg(II)-amended systems are not simply explained by the formation of pure MS; instead, metal-substituted FeS or coprecipitated sulfides are thought to be responsible for the significantly increased rates observed in these systems.     

Reductive dechlorination of tetrachloroethylene and trichloroethylene by mackinawite (FeS) in the presence of metals: reaction rates

Reductive dechlorination by mackinawite (FeS) is an important transformation pathway for chloroethylenes in anoxic environments. Yet, the impact of metals on reductive dechlorination is not well understood, despite their frequent cooccurrence with chloroethylenes. Fe(II), Co(II), Ni(II), and Hg(II) were evaluated for their impact on the dechlorination rates of PCE and TCE by FeS. Compared with unamended FeS batches, the dechlorination rates of both chloroethylenes decreased by addition of 0.01 M Fe(II). Relative to 0.01 M Fe(II)-added FeS batches, the dechlorination rates increased in FeS batches amended with 0.01 M of Co(II) and Hg(II), whereas the rates decreased in 0.01 M Ni(II)-added batches. While significantly impacting the dechlorination rates, the amended metals were quantitatively sequestered by FeS mainly because of formation of metal sulfides. Comparison of the dechlorination rates between metal-added FeS batches and metal sulfide batches suggests that discrete metal sulfides do not form in metal-added FeS batches. The observed exceptionally high reactivity of CoS suggests that it may be useful in reactive permeable barrier applications because of its stability in anoxic waters. The dechlorination rates of PCE and TCE significantly varied with Fe(ll) amendment concentrations (Fe(II)0), indicating the presence of different types of solid-bound Fe phases with Fe(II)o.     

Arsenate and arsenite adsorption and desorption behavior on coprecipitated aluminum:iron hydroxides

Although arsenic adsorption/desorption behavior on aluminum and iron (oxyhydr)oxides has been extensively studied, little is known about arsenic adsorption/desorption behavior by bimetal Al:Fe hydroxides. In this study, influence of the Al:Fe molar ratio, pH, and counterion (Ca2+ versus Na+) on arsenic adsorption/desorption by preformed coprecipitated Al:Fe hydroxides was investigated. Adsorbents were formed by initial hydrolysis of mixed Al3+/ Fe3+ salts to form coprecipitated Al:Fe hydroxide products. At Al:Fe molar ratios < or = 1:4, Al3+ was largely incorporated into the iron hydroxide structure to form a poorly crystalline bimetal hydroxide; however, at higher Al:Fe molar ratios, crystalline aluminum hydroxides (bayerite and gibbsite) were formed. Although approximately equal As(V) adsorption maxima were observed for 0:1 and 1:4 Al:Fe hydroxides, the As(III) adsorption maximum was greater with the 0:1 Al: Fe hydroxide. As(V) and As(III) adsorption decreased with further increases in Al:Fe molar ratio. As(V) exhibited strong affinity to 0:1 and 1:4 Al:Fe hydroxides at pH 3-6. Adsorption decreased at pH > 6.5; however, the presence of Ca2+ compared to Na+ as the counterion enhanced As( retention by both hydroxides. There was more As(V) and especially As(III) desorption by phosphate with an increase in Al:Fe molar ratio.     

Observation of surface precipitation of arsenate on ferrihydrite

X-ray diffraction and Raman spectroscopy were used in this study to characterize arsenate phases in the arsenate-ferrihydrite sorption system. Evidence has been obtained for surface precipitation of ferric arsenate on synthetic ferrihydrite at acidic pH (3-5) underthe following experimental conditions: sorption density of As/Fe approximately 0.125-0.49 and arsenic equilibrium concentration of <0.02-440 mg/L. Surface precipitation occurred under apparently undersaturated (in the bulk solution phase) conditions, and probably involved initial uptake of arsenate by surface complexation followed by transition to ferric arsenate formation on the surface as indicated by XRD analysis. At basic pH (i.e., pH 8), however, no ferric arsenate was observed in arsenate-ferrihydrite samples at a sorption density of As/Fe approximately 0.125-0.30 and an arsenic equilibrium concentration of 2.0-1100 mg/ L. At pH 8, arsenate is sorbed on ferrihydrite predominantly via surface adsorption, and the XRD patterns resemble basically that of ferrihydrite.     

Sonolytic desorption of mercury from aluminum oxide: effects of pH, chloride, and organic matter

The effects of pH, Cl-, and humic acid (HA) on sonolytic desorption of Hg(II) from aluminum oxide were examined. Results showed that Hg(II) desorption was achieved by lowering the pH from 7.0 to 4.0. Ultrasound enhanced Hg(II) release at short times compared to both hydrodynamic mixing and that expected on the basis of the pH-dependent Hg(II) adsorption curve. However, prolonged sonication led to decreases in Hg(II) desorption due to occlusion by aluminum hydroxide precipitation induced by ultrasound. The presence of Cl- greatly improved Hg(II) desorption at pH 4.0 due to the formation of stable nonadsorbing HgCl2(0) complexes at low pH, reducing free Hg(II) ion in solution. However, Cl- did not affect Hg(ll) desorption at pH 8.0, where Hg(OH)2(0) is the dominant Hg species rather than HgCl2(0). Hg(ll) desorption from HA-laden Al2O3 was dominated by HA. The greater the desorption of HA, the greater the desorption of Hg(II). Ultrasound enhanced the initial Hg(II) release by facilitating HA desorption. However, decreases in Hg(II) desorption were observed over longer sonication times due to the sonochemically induced reassociation of desorbed HA back onto Al2O3. Information obtained in this study provides insight into understanding sonolytic release of Hg from Hg-contaminated particles and sediments.     

Enhancement of biological reduction of hematite by electron shuttling and Fe(II) complexation

Natural organic matter (NOM) enhancement of the biological reduction of hematite (alpha-Fe2O3) by the dissimilatory iron-reducing bacterium Shewanella putrefaciens strain CN32 was investigated under nongrowth conditions designed to minimize precipitation of biogenic Fe(II). Hydrogen served as the electron donor. Anthraquinone-2,6-disulfonate (AQDS), methyl viologen, and methylene blue [quinones with an Ew0 (pH 7) of 0.011 V or less], ferrozine [a strong Fe(II) complexing agent], and characterized aquatic NOM (Georgetown NOM or Suwannee River fulvic acid) enhanced bioreduction in 5-day experiments whereas 1,4-benzoquinone (Ew0 value = 0.280 V) did not. A linear relationship existed between total Fe(II) produced and concentrations of ferrozine or NOM but not quinones, except in the case of methylene blue. Such a linear relationship between Fe(II) and methylene blue concentrations could be due to the systems being far undersaturated with respect to methylene blue or the loss of the thermodynamic driving force. A constant concentration of AQDS and variable concentrations of ferrozine produced a linear relationship between total Fe(II) produced and the concentration of ferrozine. Enhancement effects of both AQDS and ferrozine were additive. NOM may serve as both an electron shuttle and an Fe(II) complexant; however, the concentration dependence of hematite reduction with NOM was more similar to ferrozine than quinones. NOM likely enhances hematite reduction initially by electron shuttling and then further by Fe(II) complexation, which prevents Fe(II) sorption to hematite and cell surfaces.     

Sorption mechanisms of zinc on hydroxyapatite: systematic uptake studies and EXAFS spectroscopy analysis

The systematics and mechanisms of Zn uptake by hydroxyapatite (HAP) in preequilibrated suspensions open to PCO2 were characterized using a combination of batch sorption experiments, X-ray diffraction (XRD), and extended X-ray absorption fine structure spectroscopy (EXAFS) over a wide range of pH and Zn concentrations. Sorption isotherms of Zn(II) on HAP at pH 5.0 and 7.3 show an initial steep slope at low Zn(II) concentrations, followed by a plateau up to [Zn] < approximately 750 microM, suggesting Langmuir-type behavior. At [Zn] > 750 microM, a sharp rise in the pH 5.0 isotherm suggests precipitation, whereas slight continued uptake in the pH 7.3 isotherm is suggestive of an additional uptake mechanism. The sorption isotherm at pH 9.0 shows a steep uptake step at [Zn] < or = 0.8 microM, followed by an increasing linear trend up to [Zn] = 5 microM, without any indication of a maximum, suggesting that precipitation is an important uptake process at this pH. Zn K edge EXAFS results show a first oxygen shell at 1.96-1.98 +/- 0.02 A in sorption samples with [Zn]tot < or = 250 microM at pH 5.0, 7.3, and 9.0, consistent with tetrahedral coordination. EXAFS results reveal additional P and Ca neighbors that support formation of an inner-sphere Zn surface complex where the Zn is coordinated to surface P04 tetrahedra in a corner-sharing bidentate fashion, bridging a Ca atom. In contrast, EXAFS and XRD data indicate that precipitation of Zn3(PO4)2-4H2O (hopeite) dominates the mode of Zn uptake at [Zn]tot > or = 3 mM at pH 5.0. Principal component analysis and linear combination fits of EXAFS data reveal a mixture of inner-sphere Zn surface complexation and precipitation of Zn5(OH)6(CO3)2 (hydrozincite) in sorption samples for [Zn]tot = 5 mM at pH 7.3 and for [Zn]tot = 1 mM at pH 9.0.     

Hg(II) adsorption by bacteria: a surface complexation model and its application to shallow acidic lakes and wetlands in Kejimkujik National Park, Nova Scotia, Canada

The fate and environmental threat posed by mercury in aquatic systems is controlled, in part, bythe transport of Hg(II) from oxic to anoxic zones in lakes and its subsequent transformation to organic mercury. The transport of Hg(II) in aquatic systems can be affected by its partitioning between the dissolved and particulate phases. In this study, batch experiments were performed to quantify Hg(II) adsorption to Bacillus subtilis as bacteria-to-metal ratio, pH, chloride concentration, growth phase, and reaction time were independently varied. The laboratory data were well described by a surface complexation model (SCM) considering the adsorption of neutral Hg(II) hydroxide and chloride complexes by specific functional groups on the bacterial surface. To evaluate its applicability to complex aquatic systems, the SCM was used to predict the distributions of Hg(II) in 36 shallow acidic lakes and wetlands in Kejimkujik National Park, Nova Scotia, Canada. The lab-derived SCM provided a statistically accurate (r2 = 0.615, P < 0.01) fit to the field data when it was expanded to consider Hg(II) complexation by dissolved organic matter. Inclusion of Hg(II)-mineral adsorption reactions did not improve the fit of the model. The quality of fit provided by the expanded SCM suggested that the major assumptions implicit in applying a lab-derived model to the field were justifiable. Our study has demonstrated that SCMs are powerful tools for dynamic prediction of the sorption of environmental contaminants to biocolloids at the regional scale.     

Immobilization of Hg(II) by coprecipitation in sulfate-cement systems

Uptake and molecular speciation of dissolved Hg during formation of Al- or Fe-ettringite-type and high-pH phases were investigated in coprecipitation and sorption experiments of sulfate-cement treatments used for soil and sediment remediation. Ettringite and minor gypsum were identified by XRD as primary phases in Al systems, whereas gypsum and ferrihydrite were the main products in Hg-Fe precipitates. Characterization of Hg-Al solids by bulk Hg EXAFS, electron microprobe, and microfocused-XRF mapping indicated coordination of Hg by Cl ligands, multiple Hg and Cl backscattering atoms, and concentration of Hg as small particles. Thermodynamic predictions agreed with experimental observations for bulk phases, but Hg speciation indicated lack of equilibration with the final solution. Results suggest physical encapsulation of Hg as a polynuclear chloromercury(II) salt in ettringite as the primary immobilization mechanism. In Hg-Fe solids, structural characterization indicated Hg coordination by O atoms only and Fe backscattering atoms that is consistent with inner-sphere complexation of Hg(OH)(2)(0) coprecipitated with ferrihydrite. Precipitation of ferrihydrite removed Hg from solution, but the resulting solid was sufficiently hydrated to allow equilibration of sorbed Hg species with the aqueous solution. Electron microprobe XRF characterization of sorption samples with low Hg concentration reacted with cement and FeSO(4) amendment indicated correlation of Hg and Fe, supporting the interpretation of Hg removal by precipitation of an Fe(III) oxide phase.     

Kinetics and mechanisms for reactions of Fe(II) with iron(III) oxides

Uptake of Fe(II) onto hematite (alpha-Fe2O3), corundum (alpha-Al2O3), amorphous ferric oxide (AFO), and a mixture of hematite and AFO was measured. Uptake was operationally divided into adsorption (extractable by 0.5 N HCl within 20 h) and fixation (extractable by 3.0 N HCl within 7 d). For 0.25 mM Fe(II) onto 25 mM iron(III) hematite at pH 6.8: (i) 10% of Fe(II) was adsorbed within 1 min; (ii) 20% of Fe(II) was adsorbed within 1 d; (iii) uptake slowly increased to 24% of Fe(II) during the next 24 d, almost all adsorbed; (iv) at 30 d, the uptake increased to 28% of Fe(II) with 6% of total Fe(II) fixed; and (v) uptake slowly increased to 30% of Fe(II) by 45 d with 10% of total Fe(II) fixed. Similar results were observed for 0.125 mM Fe(II) onto 25 mM iron(III) hematite, except that percent of adsorption and fixation were increased. There was adsorption but no fixation for 0.25 mM Fe(II) onto corundum [196.2 mM Al(III)] at pH 6.8, for 0.125 mM Fe(II) onto 25 mM iron(III) hematite at pH 4.5, and for 0.25 mM Zn(II) onto 25 mM iron(III) hematite at pH 6.8. A small addition of AFO to the hematite suspension increased Fe(II) fixation when 0.25 mM Fe(II) was reacted with 25 mM iron(III) hematite and 0.025 mM Fe(III) AFO at pH 6.8. Reaction of 0.125 mM Fe(II) with 2.5 mM Fe(III) AFO resulted in rapid adsorption of 30% of added Fe(II), followed by conversion of AFO to goethite and a decrease in adsorption without Fe(II) fixation. The fixation of Fe(II) by hematite at pH 6.8 is consistent with interfacial electron transfer and the formation of new mineral phases. We propose that electron transfer from adsorbed Fe(II) to structural Fe(III) in hematite results in oxidation of Fe(II) to AFO on the surface of hematite and that solid-phase contact among hematite, AFO, and structural Fe(II) produces magnetite (Fe3O4). The unique interactions of Fe(II) with iron(III) oxides would be environmentally important to understand the fate of redox-sensitive chemicals.     

Formation of metal-arsenate precipitates at the goethite-water interface

Little information is available concerning cosorbing oxyanion and metal contaminants in the environment, yet in most metal-contaminated areas, cocontamination by arsenate [AsO4, As(V)] is common. This study investigated the cosorption of As(V) and Zn on goethite at pH 4 and 7 as a function of final solution concentration. Complimentary extended X-ray absorption fine structure (EXAFS) spectroscopic data were collected at the As and Zn K-edges in order to glean information about the coordination environment of As and Zn at the goethite-water interface. Macroscopic sorption studies revealed that As(V) and Zn sorption on goethite increased in cosorption experiments beyond that suggested by single sorption isotherms. At pH 4 and 7, As(V) surface saturation was 3.2 and 2.2 micromol m(-2), respectively, and Zn surface saturation was absent at pH 4 and approximately 1.0 micromol m(-2) at pH 7. Arsenate sorption on goethite increased in the presence of Zn by 29% and by more than 500% at pH 4 and 7, respectively. In the presence of As(V), Zn sorption on goethite increased by 800 and 1300% at pH 4 and 7, respectively. More As(V) than Zn sorbed on goethite below surface saturation at pH 7. Above surface saturation, the Zn:As surface density ratio (SDR) remained constant at 0.91 +/- 0.03. At pH 4, the Zn:As SDR was less than 1 throughout the concentration range. Below As(V) surface saturation on goethite, As(V) formed bidentate binuclear bridging complexes on Fe and/or Zn octahedra, while Zn mainly formed edge-sharing complexes with Fe at the goethite surface. Above surface saturation, Zn was increasingly complexed by AsO4, gradually forming an adamite-like [Zn2(AsO4)OH] surface precipitate on goethite. Precipitated contaminants are more stable due to the limited dissolution kinetics of their solid phase. This study may therefore prove useful in remediation strategies of sites knowingly contaminated with oxyanions and metals.     

Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NOx concentration

We report secondary organic aerosol (SOA) yields from the ozonolysis of alpha-pinene in the presence of NO and NO2. Experimental conditions are characterized by the [VOC]0/ [NOx]0 ratio (ppbC/ppb), which varies from approximately 1 to approximately 300. SOA yield is constant for [VOC]0/[NOx]0 > approximately 15 and decreases dramatically (by more than a factor of 4) as [VOC]0/[NOx]0 decreases. Aerosol production is completely suppressed in the presence of NO for [VOC]0/[NOx]0 < or = 4.5. Fouriertransform IR analysis of filter samples reveals that nitrate-containing species contribute significantly to the total aerosol mass at low [VOC]0/[NOx]0. Yield reduction is a result of the formation of a more volatile product distribution as [VOC]0/[NOx]0 decreases; we propose that the change in the product distribution is driven by changes in the gas-phase chemistry as NOx concentration increases. We also present two-product model parameters to describe aerosol production from the alpha-pinene/0/NOx system under both high- and low-NOx conditions.     

Co-removal of hexavalent chromium through copper precipitation in synthetic wastewater

The mechanisms of hexavalent chromium [Cr(VI)] co-removal with copper [Cu(II)] during homogeneous precipitation were studied with batch tests using a synthetic solution containing Cr(VI) and Cu(II). Metal precipitation was induced by adding Na2CO3 stepwise to different pH, and the respective removals of Cu(II) and Cr(VI) were measured. At the same time, the relative quantities of Cu(II) and Cr(VI) in the precipitates were also analyzed to establish their stoichiometric relationship. The results indicated that, in a solution containing 150 mg/L Cu(II) and 60 mg/L Cr(VI), the initial co-removal of Cr(VII with Cu(II) began at pH 5.0 and completed at pH 6.2. At pH 5.0-5.2, coprecipitation took place through the formation of copper-chromium-bearing solids [such as CuCrO4 and/or CuCrO4 x 2Cu(OH)2]. Thereafter, the remaining soluble copper started to react with carbonate in a heterogeneous environment to form the negatively charged basic copper carbonate precipitates [CuCO3 x Cu(OH)2], which subsequently adsorbed additional Cr(VI) (or HCrO4-) at pH 5.2-6.2. The maximum Cr(VI) co-removal took place at pH 6.2. Between the two mechanisms, co-precipitation accounted for about 29% of the total chromium's co-removal while the remaining 71% was attributed to surface adsorption, mainly through electrostatic attraction and ligand exchange. When the solution pH was increased to beyond 7.5, a surface charge reversal took place on the basic copper carbonate solids, and this led to some Cr(VI) desorption. Thus, the extent of Cr(VI) adsorption is highly pH dependent.     

Use of chitosan for the removal of metal ion contaminants and proteins from water

Naturally abundant biosorbants such as chitin and chitosan are recognized as excellent metal ligands, forming stable complexes with many metal ions, and serving as effective protein coagulating agents. Chitin isolated from crab processing discards was deacetylated over different time periods in order to obtain three types of chitosans [Type 1 (20 h), Type 2 (10 h) and Type3 (4 h)]. Chitosans so prepared were evaluated for their capacity to chelate metal ions in samples of water obtained from a zinc mining site (Buchans, Newfoundland). Metal chelation capacity of chitosan for wastewater was determined by inductively coupled plasma-mass spectrometry (ICP-MS) at three different pH (5, 6 and 7). Chitosan served as an effective coagulating agent in removing proteins from wastewater as well as for the removal of metal ions [Hg(II), Fe(II), Ni(II), Pb(II), Cu(II) and Zn(II)] from industrial wastewater, especially at pH 7, as measured by ICP-MS. Mercury was best chelated by all three types of chitosan under all pH conditions tested. In the protein flocculation study, Type 1 chitosan showed the best flocculation ability followed by Type 2 and Type 3 chitosans.     

Inhibition of biological reductive dissolution of hematite by ferrous iron

Bacterial dissimilatory iron reduction is self-inhibited by the production of ferrous [Fe(II)] iron resulting in diminished iron reduction as Fe(II) accumulates. Experiments were conducted to investigate the mechanisms of Fe(II) inhibition employing the dissimilatory metal-reducing bacterium Shewanella putrefaciens strain CN32 under nongrowth conditions in a system designed to minimize precipitation of ferrous iron minerals. After an initial period (ca. 1 day) of relatively rapid iron reduction, hematite reduction rates were controlled by mass transfer of Fe(II). Experiments in which hematite was equilibrated with Mn(II) prior to inoculation indicated that the observed inhibition was not due to Fe(II) sorption. At longer times, soluble Fe(II) accumulated such that the reaction was slowed due to a decreased thermodynamic driving force. The thermodynamic evaluation also supported the prior conclusion that hydrated hematite surface sites may yield substantially more energy during bioreduction than "bulk" hematite. For well-mixed conditions, the rates of hematite reduction were directly proportional to the biologically available reaction potential.