Effects of dissolved oxygen, pH, and anions on the 2,3-dichlorophenol degradation by photocatalytic reaction with anodic TiO(2) nanotube films

In this study, the highly-ordered TiO(2) nanotube (TNT) arrays on titanium sheets were prepared by an anodic oxidation method. Under UV illumination, the TNT films demonstrated the higher photocatalytic activity in terms of 2,3-dichlorophenol (2,3-DCP) degradation in aqueous solution than the conventional TiO(2) thin films prepared by a sol-gel method. The effects of dissolved oxygen (DO) and pH on the photocatalytic degradation of 2,3-DCP were investigated. The results showed that the role of DO in the 2,3-DCP degradation with the TNT film was significant. It was found that 2,3-DCP in alkaline solution was degraded and dechlorinated faster than that in acidic solution whereas dissolved organic carbon removal presented an opposite order in dependence of pH. In the meantime, some main intermediate products from 2,3-DCP degradation were identified by a (1)H NMR technique to explore a possible degradation pathway. A major intermediate, 2-chlororesorcinol, was identified from the 2,3-DCP decomposition as a new species compared to the findings in previous reports. Photocatalytic deactivation was also evaluated in the presence of individual anions (NO(3)(-), Cl(-), SO(4)(2-), and H(2)PO(4)(-)). The inhibition degree of photocatalytic degradation of 2,3-DCP caused by these anions can be ranked from high to low as SO(4)(2-)>Cl(-)>H(2)PO(4)(-)>NO(3)(-). The observed inhibition effect can be attributed to the competitive adsorption and the formation of less reactive radicals during the photocatalytic reaction.     

Changes in water-extractability of soil inorganic phosphate induced by chloride and sulfate salts

GOAL, SCOPE AND BACKGROUND: One of the principal experimental variables which effect the results of phosphorus (P) sorption studies is the ionic composition, in addition to both species and concentrations of the contacting solution. In spite of the realization that ionic species, concentrations and their compositions effect P sorption and/or desorption, most of the salt-related studies are confined to Cl- (anion) in association with different cations. While the knowledge about the comparative response of P to Cl- and SO4(2-) ions was lacking, the current study was conducted to evaluate the comparative effects of anions (in association with cations) on inorganic P release and P fractions in the soil. METHODS: The test soil was amended with livestock compost manure (OP); KH2PO4 (IPk) or Ca(H2PO4)2 (IPc) at a rate of 1ppm. Soil was subjected to one salt and nine subsequent water extractions and different P fractions were measured. Four salt types, NaCl, Na2SO4, KCl and K2SO4, were used at levels of 0.5 M. RESULTS: Irrespective of P sources, P release was substantially increased in the salt-pretreated soil as compared to the non-saline soil. Sulfate salts released more P in subsequent water extractions than Cl-. Phosphorus release decreased for salt types with Na2SO4 > NaCl > K2SO4 > KCl and for P sources with OP approximately IPk > Control (without P application) > IPc, respectively. DISCUSSION: No previous study was found to compare the results of more P release by SO4(2-) than Cl- salt. Most of the previous studies focused on anion sorption capacities, but the mechanism for their adsorption is not fully known. Most of the authors suggested that the mechanisms of SO4(2-) and PO4(3-) adsorption are similar, and that both ions compete for the same sorption sites (Kamprath et al. 1956, Couto et al. 1979, Pasricha and Fox 1993). Although adsorbed SO4(2-) does not compete strongly with PO4(3-), there is likely to be some competition for sorption between these anions which may cause comparatively more P release by SO4(2-) than Cl- salts. Higher P release by Na-saturation could be due to the release of P associated with oxide surfaces or due to dissolution of Ca-P phases (Curtin et al. 1987). CONCLUSIONS: Study clearly showed that not only cations species differ for P desorption capacity, but associated anions also play a vital role in the fate of P under saline environments. Synergetic effects exist between Na and SO4(2-) ions which enhanced the P release. This study has also confirmed the fact that P from organic sources is available as well as from inorganic P sources. However, P release depends more on the type of P source applied than on total P. RECOMMENDATIONS AND PERSPECTIVES: It is highly recommended that more than one anion species must be used in the research plans for evaluating the P response in a saline environment. The results have important implications from the point of view of research, as most of the researchers focus on different cations only for evaluating P response to salts from an environmental point of view. However, our study has made it clear that anions in association with cations differed for their effects on P release.     

Composition of wet and bulk deposition in Erzurum, Turkey

Seasonal variations in the chemical characteristics of wet and bulk deposition samples collected in Erzurum were investigated for the period March 2002-January 2003. Major cations (Ca2+, K+, Mg2+) and major anions (SO4(2-),NO3-) were determined in bulk and wet deposition samples; pH was also measured in wet deposition. The average pH of the wet deposition at Erzurum was 6.6 due to extensive neutralization of the acidity. A strong relationship between pH and SO4(2-) concentrations was observed in all seasons; however, only a weak relationship was found between pH and NO3-. On a seasonal basis, the correlation between Ca2+ and SO4(2-) concentrations was stronger in winter than in summer. Seasonal variations of ions were examined in both wet and bulk deposition samples. Although maximum concentrations of anions generally occurred during winter and spring, cation concentrations peaked in summer for both wet and bulk deposition. Results indicated that Ca2+ was the dominant cation and SO4(2-) the dominant anion in all deposition samples at Erzurum. Even though correlations among the crustal ions (calcium, magnesium and potassium) were high, the relationship between anthropogenic ions (sulfate and nitrate) was less clear in bulk deposition.     

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.     

Evaluation of the multiple-ion competition in the adsorption of As(V) onto reclaimed iron-oxide coated sands by fractional factorial design

This study describes the competitive effects of selected ions and natural organic matter on As(V) removal using reclaimed iron-oxide coated sands (RIOCS) in the single- and multi-ion systems. A 2(7-3) factional factorial experimental design (FFD) was employed for screening main competitive factors in this adsorption process. As a result, the inhibitive competition effects of the anions on As(V) removal in the single ion system were in the following sequence: PO(4)(3-)>SiO(3)(2-)>HCO(3)(-)>humic acid (HA)>SO(4)(2-)>Cl(-), whereas the cation Ca(2+) was observed to enhance the As(V) removal. In addition, the optimum initial pH for As(V) removal in single-ion system was 5. Based on the estimates of major effects and interactions from the FFD, PO(4)(3-), SiO(3)(2-), Ca(2+) and HA were important factors on As(V) removal in the multi-ion system. The promoters for the As(V) removal were found to be Ca(2+) and, to a lesser extent, SO(4)(2-). The competitive effects of these ions on As(V) removal were in the order of PO(4)(3-), SiO(3)(2-), HA, HCO(3)(-), and Cl(-). In the single ion system, the efficiencies of As(V) removal range from 75% to 96%, much higher than those in the multi-ion system (44%) at the initial pH 5. Clearly, there were some complex anion interactions in the multi-ion system. To promote the removal of As(V) by RIOCS, it is proposed to lower the pH in the single-ion system, while in the multi-ion system, the increase of the Ca(2+) concentration, or decreases of PO(4)(3-), SiO(3)(2-) and HA concentrations is suggested.     

Modeling competitive adsorption of molybdate, sulfate, selenate, and selenite using a Freundlich-type multi-component isotherm

This study examined the interactions of MoO4(2-) + SO4(2-), MoO4(2-) + SeO4(2-), and MoO4(2-) + SeO3(2-) systems on gamma-Al2O3 to better understand the competitive adsorption of these anions in the natural environment. The Freundlich isotherms of anionic adsorption onto gamma-Al2O3 in single and binary solutes were also investigated to estimate the competition between these anions. Experimental results indicate that a higher concentration of competitive solute yields a higher efficiency of the competitive solute's prevention of MoO4(2-) adsorption. The most significant result was found in the MoO4(2-) + SeO3(2-) system. The Freundlich isotherm constant (n) increases with the competitive solute concentration. The suitability of a Freundlich-type isotherm, the Sheindorf-Rebuhn-Sheintuch (SRS) equation, and the modified SRS equation in representing the competitive adsorption of MoO4(2-), SO4(2-), SeO4(2-), and SeO3(2-) on gamma-Al2O3 surface, was also examined. Each set of isotherm data was found to conform to linear SRS expressions, allowing competition coefficients to be derived on a concentration basis for each binary-solute system. The competition coefficient aij and relative affinity coefficients alphaij can be seen as a way to quantify competitive interactions. The proposed SRS and modified SRS equations are simple mathematical expressions accounting for competitive interactions of anions present in a mixture for the range of concentrations over which each individual component exhibits Freundlich behavior.     

Electrochemical monitoring of methylparathion degradation in an acid aqueous medium in presence of Cu(II)

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o,4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2-7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH < or = 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 x 10(-3) s(-1) at pH 2, 5.5 x 10(-3) s(-1) at pH 4 and 9.0 x 10(-3) s(-1) at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Geochemistry of inorganic arsenic and selenium in a tropical soil: effect of reaction time, pH, and competitive anions on arsenic and selenium adsorption

Factors that can affect As and Se adsorption by soils influence the bioavailability and mobility of these elements in the subsurface. This research attempted to compare the adsorption capacities of As(III), As(V), Se(IV), and Se(VI) on a tropical soil commonly found in Singapore in a single-species system. The effect of reaction time, pH, and competitive anions at different concentrations on the adsorption of both As and Se species were investigated. The As and Se adsorption isotherm were also obtained under different background electrolytes. The batch adsorption experiments showed that the sequence of the As and Se adsorption capacities in the soil was As(V) > Se(IV) > As(III) > Se(VI). The adsorption kinetics could be best described by the Elovich equation. The adsorption of As(V), Se(IV), and Se(VI) appeared to be influenced by the variable pH-dependent charges developed on the soil particle surfaces. Phosphate had more profound effect than SO4(2-) on As and Se adsorption in the soil. The competition between PO4(3-) and As or Se oxyanions on adsorption sites was presumably due to the formation of surface complexes and the surface accumulation or precipitation involving PO4(3-). The thermodynamic adsorption data for As(V) and Se(IV) adsorption followed the Langmuir equation, while the As(III) and Se(VI) adsorption data appeared to be best-represented by the Freundlich equation.     

Hydroxyl radical scavenging role of chloride and bicarbonate ions in the H2O2/UV process

Simultaneous effect of inorganic anions, such as chloride and bicarbonate ions, on the scavenging of hydroxyl radicals (HO*) in the H2O2/UV process is the focus of this paper. The model compound of n-chlorobutane (BuCl) was used as the probe of HO*. By changing the pH conditions (2-9) and the concentrations of NaCl (0.25-2500 mM) and NaHCO3 (25 mM), the variation of HO* concentrations and the rate of H2O2 decomposition were compared. In general, the BuCl and H2O2 follow closely the first-order reaction within the first 10 and 40 min, respectively. In the presence of chloride alone at the pH range of 2-6, the HO* concentration in the reaction mixture increases with the increase of pH, and the HO* concentration at pH = 6 is 100 times of that at pH = 2. Including bicarbonate species in the solution, the peak HO* concentration was found at a certain pH, which shifts from 4, 5, to 5-7, as the molar ratios of chloride/bicarbonate species increase from 1 to 100. In addition, without bicarbonate species HO* concentration decreases significantly with increasing chloride concentration but remained rather unchanged beyond 1250 mM. In contrast, the HO* scavenging in the presence of bicarbonate species became relatively significant only when the chloride concentration reached beyond 250 mM. Throughout all experiments of different water quality conditions, the H2O2 decomposition rate remains rather unchanged.     

Application of the EPR spin-trapping technique for the investigation of the reactions of carbonate, bicarbonate, and phosphate anions with hydroxyl radicals generated by the photolysis of H2O2

The spin trapping technique with electron paramagnetic resonance (EPR) detection of spin adducts was applied for the investigation of the reaction of hydroxyl radicals, generated by the photolysis of hydrogen peroxide, with bicarbonate and carbonate anions. The results have been compared with those obtained for aqueous solutions of hydrogen peroxide as well as solutions containing phosphate buffers at pH values identical with those of the carbonate, and bicarbonate solutions. Both the carbonate, and bicarbonate anions quenched the hydroxyl radicals more efficiently than phosphate buffers. The effect depended on the anion concentrations, and it was most pronounced in the presence of carbonate. Rate constants for the reaction of OH with the investigated anions have been calculated. They are very close to values reported in the literature, obtained using optical detection of the carbonate and phosphate radicals.     

Effect of immobilized microalgal bead concentrations on wastewater nutrient removal

A unicellular green microalga, Chlorella vulgaris, entrapped in calcium alginate as algal beads were employed to remove nutrients (N and P) from simulated settled domestic wastewater. A significantly higher nutrient reduction was found in bioreactors containing algal beads (at concentrations ranging from 4 to 20 beads ml(-1) wastewater) than the blank alginate beads (without algae). A complete removal of NH(4)(+)-N and around 95% reduction of PO(4)(3-)-P was achieved within 24 h of treatment in bioreactors having the optimal algal bead concentration (12 beads ml(-1), equivalent to 1:3 algal beads:wastewater, v/v). The NH(4)(+)-N removal was significantly lower at low (around 4 beads ml(-1)) and high (>15 beads ml(-1)) algal bead concentrations. On the other hand, the effect of bead concentration on phosphate removal was less obvious, and bead concentrations ranging from 8 to 20 beads ml(-1) showed comparable percentages of phosphate reduction. Algal uptake and adsorption on alginate gels were found to be the major processes involved in the removal of N and phosphate in the present study. In addition, NH(4)(+)-N could be lost via ammonia volatilization while PO(4)(3-)-P was removed by chemical precipitation, as alkaline pH was recorded in the immobilized microalgal treatment system.     

Kinetics of the chemical degradation of diuron

The influence of pH and buffer concentration on the chemical degradation of diuron in water has been analysed over a wide temperature range. The process irreversibly gives 3,4-dichloroaniline as the only product containing the phenyl ring. H+, OH- and phosphate buffer are efficient catalysts of the reaction. The rate constant first increases rapidly at low buffer concentrations and then gradually levels off at higher ones. At 40 degrees C and high phosphate concentration (>0.01 M), or in the extreme pH regions, the half-life is approximately 4 months and the activation energy is 127 +/- 2 kJmol(-1).     

Soil solution nitrogen and cations influenced by (NH4)2SO4 deposition in a coniferous forest

The effects of chronically enhanced (NH(4))(2)SO(4) deposition on ion concentrations in soil solution and ionic fluxes were investigated in a Picea abies plot at Grizedale forest, NW England. Soil cores closed at the base and containing a ceramic suction cup sampler were 'roofed' and watered every 2 weeks with bulk throughfall collected in the field. Treatments consisted of the inclusion of living roots from mature trees in the lysimeters and increasing (NH(4))(2)SO(4) deposition (NS treatment) to ambient + 75 kg N ha(-1) a(-1). Rainfall, throughfall and soil solutions were collected every 2 weeks during 18 months, and analysed for major cations and anions. NO(3)(-) fluxes significantly increased following NS treatment, and were balanced by increased Al(3+) losses. Increased SO(4)(2-) concentrations played a minor role in controlling soil solution cation concentrations. The soil exchange complex was dominated by Al and, during the experimental period, cores of all treatments 'switched' from Ca(2+) to Al(3+) leaching, leading to mean [Formula: see text] molar ratios in soil solution of NS treated cores of 0.24. The experiment confirmed that the most sensitive soils to acidification (through deposition or changing environmental conditions) are those with low base saturation, and with a pH in the lower Ca, or Al buffer ranges.     

溶液中阴离子对UV/H2O2降解十二烷基苯磺酸钠的影响及其机理

研究了UV/H2O2工艺对十二烷基苯磺酸钠(LAS)的去除效果、溶液中阴离子对LAS降解的影响及机理.结果表明:UV/H2O2工艺可以有效地去除水中的LAS;在H2O2投加量为8 mg/L,14 W低压汞灯照射下,LAS在蒸馏水和自来水中的反应速率常数分别为0.018 0 、0.012 2 min-1;NO-3、Cl-、SO2-4和HCO-3对LAS光降解有抑制作用,当该4种离子摩尔浓度均分别为5、10、15 mmol/L时,对LAS光降解的抑制程度为HCO-3》NO-3》Cl-》SO2-4,且随着离子摩尔浓度的增大,抑制作用增强;LAS在自来水中的反应速率常数低于在蒸馏水中的反应速率常数是由于水中多种离子影响的结果.     

金属铁去除水中Cr~（6＋）的影响因素研究

研究Fe/Cr6＋比值和不同浓度的NO3-、Cl-和SO42-对金属铁去除Cr6＋效果的影响。结果表明,金属铁对水中Cr6＋有很好的还原去除效果;当金属铁的使用量为Cr6＋量的1/2 000时,铁对Cr6＋的去除效果较差且易失去活性,而当金属铁的使用量为Cr6＋量的8 000倍时,铁对Cr6＋的去除效果较好且其活性的持续性较强;3种阴离子（NO3-、Cl-和SO42-）均能提高金属铁对重金属Cr6＋去除率,但在反应初期,3种阴离子对金属铁去除水中Cr6＋影响的差异性不显著,随着反应时间的增加,SO24-对金属铁去除水中Cr6＋的促进作用逐渐强于Cl-和NO3-,3种阴离子对金属铁去除Cr6＋效率促进作用的大小顺序为SO24-〉Cl-〉NO3-。     

Effect of atmospheric N deposition on surface water chemistry and the implications for fisheries

In this paper the relative importance of NO3- and SO4(2-) as anions in oligotrophic surface waters and evidence that NO3 concentrations have been increasing in recent decades in reviewed. The relationship between NO3- and the concentrations of cations (H+ and Al3+) known to be harmful to aquatic biota is also discussed. It is generally concluded that although direct proof of an association is lacking, circumstantial evidence suggests that atmospheric input of nitrogen to soils on certain 'sensitive' geologies may be having consequences for surface waters and the biota living in them, especially at certain times of the year, e.g. snowmelt.     

Effects of various ions on the dechlorination kinetics of hexachlorobenzene by nanoscale zero-valent iron

The effect of several anions and cations normally co-present in soil and groundwater contamination sites on the degradation kinetics and removal efficiency of hexachlorobenzene (HCB) by nanoscale zero-valent iron (NZVI) particles was examined. The degradation kinetics was not influenced by the HCO(3)(-), Mg(2+), and Na(+) ions. It was enhanced in the presence of the Cl(-) and SO(4)(2-) ions due to their corrosion promotion. The NO(3)(-) competes with HCB so it inhibits the degradation reaction. The Fe(2+) ions would inhibit the degradation reaction due to passivation layer formed, while it was enhanced in the presence of Cu(2+) ions resulted from the reduced form of copper on NZVI surfaces. These observations lead to a better understanding of HCB dechlorination with NZVI particles and can facilitate the remediation design and prediction of treatment efficiency of HCB at remediation sites.     

Dynamics of nitrogen in a PAHs contaminated soil amended with biosolid or vermicompost in the presence of earthworms

Nitrogen mineralization in PAHs contaminated soil in presence of Eisenia fetida amended with biosolid or vermicompost was investigated. Sterilized and unsterilized soil was contaminated with PAHs, added with E. fetida and biosolid or vermicompost and incubated aerobically for 70 days, while dynamics of inorganic N were monitored. Addition of E. fetida to sterilized soil increased concentration of NH(4)(+) 100> mg N kg(-1), while concentrations in unsterilized remained <60 mg N kg(-1) except for soil amended with biosolid plus PAHs where it increased to >80 mg kg(-1). Addition of PAHs had no significant effect on concentration of NH(4)(+) compared to the unamended soil, except in the soil added with biosolid. Addition of E. fetida to sterilized soil increased concentration of NO(2)(-) 15> mg N kg(-1) while concentrations in unsterilized soil remained <7.5 mg N kg(-1) except for soil amended with biosolid where it increased to >20 mg kg(-1). Addition of PAHs had no significant effect on concentration of NO(2)(-) compared to the unamended soil. Addition of biosolid and vermicompost increased concentration of NO(3)(-), while addition of E. fetida decreased concentration of NO(3)(-) in biosolid amended soil. It was found that NH(4)(+) and NO(2)(-) oxidizers were present in the gut of E. fetida, but their activity was not sufficient enough to inhibit a temporarily increase in concentrations of NH(4)(+) and NO(2)(-). Contamination with PAHs induced immobilization of N in biosolid or vermicompost amended soil, as did feeding of E. fetida on biosolid or vermicompost.     

Trace metals, anions and polybromodiphenyl ethers in settled indoor dust and their association

Contaminants in settled indoor dust are potentially health hazardous to human. Thus, identification and quantification of toxic chemicals in settled indoor dust is of great concern. In this study, the levels of major anions ( $ \mathrm{C}{{\mathrm{l}}^{-}},\mathrm{N}{{\mathrm{O}}_2}^{-},\mathrm{B}{{\mathrm{r}}^{-}},\mathrm{N}{{\mathrm{O}}_3}^{-},\mathrm{P}{{\mathrm{O}}_4}^{3-}\,\mathrm{and}\,\mathrm{S}{{\mathrm{O}}_4}^{2- } $ ), trace metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, As and Pb) and polybromodiphenyl ethers (PBDEs) in settled office and home dust were determined and correlations between the contaminants investigated. Depending on the available materials in both microenvironments, the most possible sources were identified. The results showed that the settled office dusts (n?=?6 pooled samples from 85 offices) were more contaminated than home dusts (n?=?8 homes). For anions, $ \mathrm{S}{{\mathrm{O}}_4}^{2- } $ and Cl^– accounted for 87 and 97 % of the total office and home dust contaminants, respectively. For trace metals, Fe, Cu, Zn and Mn, accounted for 98 % of the contaminants in both office and home dust samples. Fe exhibited the highest percentage of 76.7 and 87.3 % in office and home dust samples, respectively. For PBDEs, the mean concentrations detected in office and home dust ranged between 5.8–86.3 and 1.5–20.6 ng?g^?1, respectively. The log-transformed correlation between the total concentrations of trace metals and major anions detected in offices and homes was positive for offices and negative for homes with a statistically significant values (r?=?0.73, p?<?0.01; r?= ?0.22, p?<?0.01, respectively). The daily exposure rates determined for the most hazardous such as As, Cd, Pb and PBDEs congeners, relative to the individual concentrations reported in the literature in settled indoor dust, were found very lower. Therefore, maybe it is possible to expect less potential health risk. Investigation of formation of coordination compounds between trace metals and PBDEs congeners is possible; however, this requires further study.     

Adsorption of molybdate and tetrathiomolybdate onto pyrite and goethite: effect of pH and competitive anions

The adsorption of two major molybdenum (Mo) species, molybdate (MoO4(2-)) and tetrathiomolybdate (MoS4(2-)) onto two main iron minerals pyrite (FeS2) and goethite (FeOOH) is addressed to elucidate the possible mechanisms of molybdenum immobilization in anoxic sediments. Suspensions of MoS4(2-) (or MoO4(2-)) and goethite (or pyrite) in 0.1M NaCl solution were equilibrated under anoxic conditions at 25 degrees C in the pH range from 3 to 10. The competitive effects of sulfate, phosphate, and silicate on the adsorption of MoO4(2-) and MoS4(2-) by pyrite and goethite are also addressed. Adsorption of MoO4(2-) and MoS4(2-) on pyrite and goethite is in general well described by a Langmuir model at low pH; the extent of sorption is a function of pH and the surface loading. Maximum sorption is observed in the acidic pH range (pH<5) at low surface loading. The adsorption of molybdenum (micromol g(-1)) depends upon Mo species and on the type of iron mineral following the order: MoS4(2-)-goethite > MoO4(2-)-goethite > MoS4(2-)-pyrite > MoO4(2-)-pyrite. Phosphate appears to compete strongly with MoO4(2-) and MoS4(2-) for the sorption sites of pyrite and goethite. The strength of the phosphate competitive effect follows the sequence of MoO4(2-)-goethite approximately = MoO4(2-)-pyrite > MoS4(2-)-pyrite > MoS4(2-)-goethite. Silicate and sulfate have a negligible effect on the sorption of MoO4(2-) and MoS4(2-). The preferred adsorption by iron mineral of MoS4(2-), as well as its behavior in the presence of competitive anions suggests that tetrathiomolybdate species may be an ultimate reservoir and may control Mo enrichment in the sediments.