Investigation of the removal mechanism of Cr(VI) in groundwater using activated carbon and cast iron combined system

Zero-valent iron (Fe⁰) has been widely used for Cr(VI) removal; however, the removal mechanisms of Cr(VI) from aqueous solution under complex hydrogeochemical conditions were poorly understood. In this research, the mixed materials containing cast iron and activated carbon were packed in columns for the treatment of aqueous Cr(VI)-Cr(III) in groundwater with high concentration of Ca²⁺, Mg²⁺, HCO₃ ⁻, NO₃ ⁻, and SO₄ ²⁻. We investigate the influences of those ions on Cr(VI) removal, especially emphasizing on the reaction mechanisms and associated precipitations which may lead to porosity loss by using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) techniques. The results show that the precipitations accumulated on the material surface were (Fe/Cr) (oxy)hydroxide, mixed Fe(III)-Cr(III) (oxy)hydroxides, Fe₂O₃, CaCO₃, and MgCO₃. During these reactions, the Cr(VI) was reduced to Cr(III) coupled with the oxidated Fe⁰ to Fe(II) through the galvanic corrosion formed by the Fe⁰-C and/or the direct electron transfer between Fe⁰ and Cr(VI). In addition, Cr(VI) could be reduced by aqueous Fe(II), which dominated the whole removal efficiency. The primary aqueous Cr(III) was completely removed together with Cr(III) reduced from Cr(VI) even when Cr(VI) was detected in the effluent, which meant that the aqueous Cr(III) could occupy the adsorption sites. In general, the combined system was useful for the Cr(VI)-Cr(III) treatment based on galvanic corrosion, and the hardness ions had a negative effect on Cr(VI) removal by forming the carbonates which might promote the passivation of materials and decrease the removal capacity of the system.

     

A synergism between ultraviolet and gamma radiation in producing aerosol particles from SO2H2SO4 laden atmospheres

Experiments were performed to compare the capability of u.v. light, γ-radiation and simultaneous u.v. and γ-radiation to produce aerosol particles in a mixture of SO₂, NO₂ and synthetic air at different humidities. In the presence of u.v. radiation, γ-radiation was found to enhance the particle production at dose rates as low as 10⁻⁴ μGy s⁻¹ at 0% r.h., and 2 × 10⁻² μGy s⁻¹ at 75% r.h. γ-radiation alone did not produce aerosol particles at the same dose rates. The possible processes underlying this synergistic effect are discussed.     

Synthesis of α-Fe2O3 nanofibers for applications in removal and recovery of Cr(VI) from wastewater

Purpose

Nanomaterials such as iron oxides and ferrites have been intensively investigated for water treatment and environmental remediation applications. The purpose of this work is to synthesize α-Fe₂O₃ nanofibers for potential applications in removal and recovery of noxious Cr(VI) from wastewater.

Methods

α-Fe₂O₃ nanofibers were synthesized via a simple hydrothermal route followed by calcination. The crystallographic structure and the morphology of the as-prepared α-Fe₂O₃ nanofibers were characterized by X-ray diffraction, scanning electron microscope, and transmission electron microscope. Batch adsorption experiments were conducted, and Fourier transform infrared spectra were recorded before and after adsorption to investigate the Cr(VI) removal performance and adsorption mechanism. Langmuir and Freundlich modes were employed to analyze the adsorption behavior of Cr(VI) on the α-Fe₂O₃ nanofibers.

Results

Very thin and porous α-Fe₂O₃ nanofibers have been successfully synthesized for investigation of Cr(VI) removal capability from synthetic wastewater. Batch experiments revealed that the as-prepared α-Fe₂O₃ nanofibers exhibited excellent Cr(VI) removal performance with a maximum adsorption capacity of 16.17 mg g^?1. Furthermore, the adsorption capacity almost kept unchanged after recycling and reusing. The Cr(VI) adsorption process was found to follow the pseudo-second-order kinetics model, and the corresponding thermodynamic parameters ΔG°, ΔH°, and ΔS° at 298 K were calculated to be ?26.60 kJ?mol^?1, ?3.32 kJ?mol^?1, and 78.12 J?mol^?1 K^?1, respectively.

Conclusions

The as-prepared α-Fe₂O₃ nanofibers can be utilized as efficient low-cost nano-absorbents for removal and recovery of Cr(VI) from wastewater.     

Preparation of a novel iron-based biochar composite for removal of hexavalent chromium in water

The chitosan-stabilized ferrous sulfide nanoparticles were loaded on biochar to prepare a composite material FeS-CS-BC for effective removal of hexavalent chromium in water. BC and FeS-CS-BC were characterized by Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. Batch experiments were employed to evaluate the Cr(VI) removal performance. The experimental results showed that the removal rate of Cr(VI) by FeS-CS-BC(FeS:CS:BC?=?2:2:1) reached 98.34%, which was significantly higher than that of BC (44.58%) and FeS (79.91%). In the pH range of 2–10, the removal of Cr(VI) by FeS-CS-BC was almost independent of pH. The limitation of coexisting anions (Cl^?、SO₄^2?、NO₃^?) on Cr(VI) removal was not too obvious. The removal of Cr(VI) by FeS-CS-BC was fitted with the pseudo-second-order dynamics, which was a hybrid chemical-adsorption reaction. The X-ray photoelectron spectroscopy (XPS) analysis result showed that Cr(VI) was reduced, and the reduced Cr(VI) was fixed on the surface of the material in the form of Cr(VI)–Fe(III).

Removal of hexavalent chromium from wastewater by FeS-CS-BC composite synthesized by impregnation.

     

Cr(VI) and COD removal from landfill leachate by polyculture constructed wetland at a pilot scale

Four subsurface horizontal-flow constructed wetlands (CWs) at a pilot scale planted with a polyculture of the tropical plants Gynerium sagittatum (Gs), Colocasia esculenta (Ce) and Heliconia psittacorum (He) were evaluated for 7 months. The CW cells with an area of 17.94 m² and 0.60 m (h) each and 0.5 m of gravel were operated at continuous gravity flow (Q?=?0.5 m³ day^?1) and a theoretical HRT of 7 days each and treating landfill leachate for the removal of filtered chemical oxygen demand (COD_f), BOD₅, TKN, NH₄ ⁺, NO₃ ^?, PO₄ ^3?–P and Cr(VI). Three CWs were divided into three sections, and each section (5.98 m²) was seeded with 36 cuttings of each species (plant density of six cuttings per square metre). The other unit was planted randomly. The final distributions of plants in the bioreactors were as follows: CW I (He-Ce-Gs), CW II (randomly), CW III (Ce-Gs-He) and CW IV (Gs-He-Ce). The units received effluent from a high-rate anaerobic pond (BLAAT®). The results show a slightly alkaline and anoxic environment in the solid-liquid matrix (pH?=?8.0; 0.5–2 mg L^?1 dissolved oxygen (DO)). COD_f removal was 67 %, BOD₅ 80 %, and TKN and NH₄ ⁺ 50–57 %; NO₃ ^? effluents were slightly higher than the influent, PO₄ ^3?–P (38 %) and Cr(VI) between 50 and 58 %. CW IV gave the best performance, indicating that plant distribution may affect the removal capacity of the bioreactors. He and Gs were the plants exhibiting a translocation factor (TF) of Cr(VI) >1. The evaluated plants demonstrated their suitability for phytoremediation of landfill leachate, and all of them can be categorized as Cr(VI) accumulators. The CWs also showed that they could be a low-cost operation as a secondary system for treatment of intermediated landfill leachate (LL).     

Trivalent chromium solubility and its influence on quantification of hexavalent chromium in ambient particulate matter using EPA method 6800

Measurement of carcinogenic Cr(VI) in ambient PM is challenging due to potential errors associated with conversion between Cr(VI) (a carcinogen) and Cr(III) (an essential nutrient). Cr(III) conversion is a particular concern due to its >80% atomic abundance in total Cr. U.S. Environmental Protection Agency (EPA) method 6800 that uses water-soluble isotope spikes can be used to correct the interconversion. However, whether the enriched Cr(III) isotope spikes can adequately mimic the Cr(III) species originally in ambient PM is unknown. This study examined the water solubility of Cr(III) in ambient PM and discussed its influence on Cr(VI) measurement. Ambient PM₁₀ samples were collected on Teflon filters at four sites in New Jersey that may have different Cr emission sources. The samples were ultrasonically extracted with 5 mL DI-H₂O (pH 5.7) at room temperature for 40 min, and then analyzed by ion chromatography–inductively coupled plasma mass spectrometry (IC-ICPMS). Cr(III) was below detection limit (0.06 ng/m³) for all samples, suggesting water-soluble Cr(III) species, such as CrCl₃, Cr(NO₃)₃, and amorphous Cr(OH)₃, in the ambient PM were negligible. Therefore, the enriched ⁵⁰Cr(III) isotope spike (in the form of Cr(NO₃)₃) could not mimic the original ambient Cr(III). Only the conversion of ⁵³Cr(VI) (in the form of K₂CrO₄) was taken into account when correcting the interconversion. We then used NaHCO₃-pretreated MCE filters (prespiked with enriched isotope species) to measure Cr(VI) in the ambient PM₁₀. The samples were ultrasonically extracted at 60 C pH 9 solutions for 40 min followed by IC-ICPMS analysis. Due to the correction of Cr(VI) reduction, the Cr(VI) concentrations determined by EPA method 6800, 0.26 ± 0.16 (summer) and 0.16 ± 0.11(winter) ng/m³ (n = 64), were significantly greater than those by the external standard curve, 0.21 ± 0.17 (summer) and 0.10 ± 0.07 (winter) ng/m³ (n = 56) (p < 0.01, Student’s t-test). Our study revealed that appropriate application of EPA method 6800 is important because it only applies to soluble fraction of Cr species in ambient PM.

ImplicationsAccurate measurement of carcinogenic Cr(VI) in ambient PM is challenging due to conversion between Cr(VI) (a human carcinogen) and Cr(III) (a human essential nutrient). The conversion of Cr(III) is of particular concern due to its dominant presence in total Cr (>80%). This study examined the water solubility of Cr(III) in ambient PM that was collected at four locations in New Jersey. Then we discussed the influence of Cr(III) solubility on the application of EPA method 6800, which utilizes enriched isotope spikes to correct the interconversion. Our results suggested that appropriate application of EPA method 6800 is important because it only applies to soluble fraction of Cr species.     

Uptake of nitrous acid and nitrogen oxides by nylon surfaces: Implications for nitric acid measurement

The interference in HNO₃ determination due to HNO₂ and NO_x retention on nylon filters has been evaluated in laboratory and field conditions. Nitrous acid is retained on nylon filters with efficiencies varying from 25% at 12ℓ min⁻¹ to 80% at 2ℓ min⁻¹, yielding NO₂⁻ ion. In ambient sampling performed during photochemical smog episodes, NO₂⁻ is oxidized to NO₃⁻ with conversion factors up to 100%, resulting in a positive bias in HNO₃ determination.NO₂ reacts heterogeneously with H₂O on nylon surfaces according to the reaction 2NO₂ + H₂O → HNO₂ + HNO₃ with a removal constant of about 1 × 10⁻⁴ ms⁻¹ at a H₂O concentration of 20,000 ppm. The resulting nitrite and nitrate are independent of the sampling flow rate, while NO₂ concentration, sampling time and exposed nylon surface area play a directly proportional role. Accordingly, the relative interference of NO₂ with respect to HNO₃ determination is almost negligible for nylon filters, usually run at relatively high flow rates, while it may be significant for nylon denuders, which are characterized by larger exposed surfaces and lower operating flow rates.     

Comparison of biochar- and activated carbon-supported zerovalent iron for the removal of Se(IV) and Se(VI): influence of pH,ionic strength,and natural organic matter

Biochar (BC) and activated carbon (AC) were both produced from corn straw. Biochar-supported zerovalent iron (BC-ZVI) and activated carbon-supported zerovalent iron (AC-ZVI) were synthesized and applied for Se(IV)/Se(VI) removal. The sorption capacity of BC-ZVI for Se(IV) and Se(VI) was reported at 62.52 and 35.39 mg g^?1, higher than that of AC-ZVI (56.02 and 33.24 mg g^?1), respectively, due to its higher iron content and more positive charges. The spectroscopic analyses showed that Se(IV)/Se(VI) were reduced to Se(0)/Se(-II) of less toxicity and solubility. The effects of various factors such as pH, ionic strength, co-existing cations and anions, and natural organic matter (NOM) were also investigated. Ionic strength showed no significant effect on Se(IV)/Se(VI) removal, but pH was critical. The presence of NO₃^? and SO₄^2? did not cause obvious inhibition to the removal, while PO₄^3? inhibited the sorption capacity of BC-ZVI and AC-ZVI for Se(IV)/Se(VI) significantly. Common cations (K⁺, Ca²⁺, and Mg²⁺) were found to slightly enhance the removal, while NOM significantly decreased the sorption capacity of BC-ZVI and AC-ZVI for Se(IV)/Se(VI). Besides, NOM showed stronger inhibition effect on AC-ZVI than that on BC-ZVI. These results indicated that BC-ZVI, compared with AC-ZVI, could be a promising sorbent to remove Se(IV)/Se(VI) due to its low cost and high efficiency.

     

Chemical composition of rainwater and anthropogenic influences in the Piracicaba River Basin,Southeast Brazil

The influences of different kinds of anthropogenic activities on rainwater chemistry in a tropical area were studied during one uninterrupted year at Piracicaba River Basin (Southeast Brazil). A total of 272 rainwater samples collected continuously from August 1997 to July 1998 at four different sites were analyzed for F⁻, CH₃COO⁻, HCOO⁻, MSA, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, SO₄²⁻, C₂O₄²⁻, PO₄³⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, DOC (dissolved organic carbon), DIC (dissolved inorganic carbon), pH and conductivity. The most abundant ion was H⁺ and rain acidity was significant at all sampling sites (average pH of 4.4–4.5). The sources of this free acidity differ among sites and appear to be correlated to the different land-uses. The composition of rainwater appeared to be controlled mostly by three sources: soil dust, sugar cane burning and industrial emissions.     

Chemical composition of the fine and coarse fraction of aerosols in the northeastern Mediterranean

Two-stage aerosol samples (PM_10–2.5 and PM_2.5) were collected at a coastal rural site located in the northeastern Mediterranean, between April 2001 and 2002. A total of 562 aerosol samples were analyzed for trace elements (Fe, Ti, Mn, Ca, V, Ni, Zn, Cr) and water-soluble ions (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, Br⁻, NO₃⁻, SO₄²⁻, C₂O₄²⁻ and MS⁻:methane sulfonate). PM₁₀, crustal elements, sea salt aerosols and NO₃⁻ were mainly associated with the coarse mode whereas non-sea salt (nss)SO₄²⁻, C₂O₄²⁻; MS⁻, NH₄⁺, Cr and Ni were found predominantly in the fine fraction. Concentrations of aerosol species exhibited orders of magnitude change from day to day and the aerosol chemical composition is heavily affected by dust events under the influence of airflow from North Africa. During the sampling period, 11 specific mineral dust events of duration varying from 1 day to a week have been identified and their influence on the chemical composition of aerosols has been studied in detail. Ionic balance analysis performed in the coarse and fine aerosol fractions indicated anion and cation deficiency due to CO₃²⁻ and H⁺, respectively. A relationship between nssSO₄²⁻ and NH₄⁺ denoted that sulfate particles were partially neutralized (70%) by ammonium. Excess-K/BC presented two distinct ratios for winter and summer, indicating two different sources: fossil fuel burning in winter and biomass burning in summer.     

Removal of Cr(VI) onto Ficus carica biosorbent from water

The utilization of sustainable and biodegradable lignocellulosic fiber to detoxify the noxious Cr(VI) from wastewater is considered a versatile approach to clean up a contaminated aquatic environment. The aim of the present research is to assess the proficiency and mechanism of biosorption on Ficus carica bast fiber via isotherm models (Langmuir, Freundlich, Temkin, Harkin’s–Jura, and Dubinin–Radushkevich), kinetic models, and thermodynamic parameters. The biomass extracted from fig plant was characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and contact time were studied by batch method. The equilibrium data were best represented by the Langmuir isotherm model, and the maximum adsorption capacity of Cr(VI) onto biosorbent was found to be 19.68 mg/g. The pseudo-second-order kinetic model adequately described the kinetic data. The calculated values of thermodynamic parameters such as enthalpy change (?H ⁰), entropy change (?S ⁰), and free energy change (?G ⁰) were 21.55 kJ/mol, 76.24 J/mol?K, and ?1.55 kJ/mol, respectively, at 30 °C which accounted for spontaneous and endothermic processes. The study of adsorbent capacity for Cr(VI) removal in the presence of Na⁺, Mg²⁺, Ca²⁺, SO ₄ ^2? , HCO ₃ ^? and Cl^? illustrated that the removal of Cr(VI) increased in the presence of HCO^3? ions; the presence of Na⁺, SO ₄ ^2? or Cl^? showed no significant influence on Cr(VI) adsorption, while Ca²⁺ and Mg²⁺ ions led to an insignificant decrease in Cr(VI) adsorption. Further, the desorption studies illustrated that 31.10 % of metal ions can be removed from an aqueous system, out of which 26.63 % of metal ions can be recovered by desorption in first cycle and the adsorbent can be reused. The results of the scale-up study show that the ecofriendly detoxification of Cr(VI) from aqueous systems was technologically feasible.     

Simultaneous removal of NOx,SO2, and Hg from flue gas in FGD absorber with oxidant injection (NaClO2)– full-scale investigation

ABSTRACT

This article presents the results of an industrial-scale study (on 400 MW_e lignite fired unit) of simultaneous NO_x, SO₂, and Hg^T removal in FGD absorber with oxidant injection (NaClO₂) into flue gas. It was confirmed that the injection of sodium chlorite upstream the FGD (Flue Gas Desulfurization) absorber oxidize NO to NO₂, Hg⁰ to Hg²⁺, and enhancing NO_x and Hg^T removal efficiency from exhaust gas in FGD absorber. Mercury removal efficiency grows with the rise of degree of oxidation NO to NO₂ and was limited by the phenomenon of re-emission. For NO_x removal the most critical parameters is slurry pH and temperature. There was no negative effect on sulfur dioxide removal efficiency caused by oxidant injection in tested FGD absorber. Based on the data provided, NO_x and Hg^T emissions can be reduced by adjusting the FGD absorber operating parameters combined with oxidant injection.     

Phytoextraction of Pb,Cr, Ni,and Zn using the aquatic plant Limnobium laevigatum and its potential use in the treatment of wastewater

In order to study the bioaccumulation of Pb, Cr, Ni, and Zn and the stress response, the floating aquatic plant Limnobium laevigatum was exposed to increasing concentrations of a mixture of these metals for 28 days, and its potential use in the treatment of wastewater was evaluated. The metal concentrations of the treatment 1 (T1) were Pb 1 μg L⁻¹, Cr 4 μg L⁻¹, Ni 25 μg L⁻¹, and Zn 30 μg L⁻¹; of treatment 2 (T2) were Pb 70 μg L⁻¹, Cr 70 μg L⁻¹, Ni 70 μg L⁻¹, and Zn 70 μg L⁻¹; and of treatment 3 (T3) were Pb 1000 μg L⁻¹, Cr 1000 μg L⁻¹, Ni 500 μg L⁻¹, and Zn 100 μg L⁻¹, and there was also a control group (without added metal). The accumulation of Pb, Cr, Ni, and Zn in roots was higher than in leaves of L. laevigatum, and the bioconcentration factor revealed that the concentrations of Ni and Zn in the leaf and root exceeded by over a thousand times the concentrations of those in the culture medium (2000 in leaf and 6800 in root for Ni; 3300 in leaf and 11,500 in root for Zn). Thus, this species can be considered as a hyperaccumulator of these metals. In general, the changes observed in the morphological and physiological parameters and the formation of products of lipid peroxidation of membranes during the exposure to moderate concentrations (T2) of the mixture of metals did not cause harmful effects to the survival of the species within the first 14 days of exposure. Taking into account the accumulation capacity and tolerance to heavy metals, L. laevigatum is suitable for phytoremediation in aquatic environments contaminated with moderated concentrations of Cr, Ni, Pb, and Zn in the early stages of exposure.

     

Trace and major elements in atmospheric deposition in the ‘Campo de Gibraltar’ region

The total (wet and dry) deposition of trace and major elements from the atmosphere was measured throughout 1 year at twelve sampling stations in the ‘Campo de Gibraltar’, an industrial zone where there are important residential areas. The data included in this paper have contributed to a better knowledge of the regional deposition of Al, Cr, Fe, Mn, Ni, Pb, V, Zn, Ca, Mg, K, Na, Cl⁻, NH₄⁺, NO₃⁻and SO₄²⁻ in both soluble and insoluble form.     

Estimation of night-time N2O5 concentrations from ambient NO2 and NO3 radical concentrations and the role of N2O5 in night-time chemistry

Dinitrogen pentoxide (N₂O₅), which is present in equilibrium with NO₃ radicals and NO₂, has been recognized for some time as an intermediate in the NO_x chemistry of night-time atmospheres. However, until the advent of long pathlength spectroscopic techniques for the measurement of atmospheric NO₃ radical concentrations, no reliable method for estimating N₂O₅ concentrations has been available. We have calculated maximum night-time N₂O₅ concentrations from the available experimentally determined concentrations of the NO₃ radical and NO₂ in the U.S. and Germany, and find that N₂O₅ concentrations as high as ~ 15 ppb can occur. We have also estimated removal rates for N₂O₅ and for NO₃ radicals during these nights. From data obtained under conditions devoid of point sources of NO_x, upper limit estimates of the homogeneous rate constant for the reaction of N₂O₅ with water vapor are obtained, leading to the conclusion that the homogeneous gas phase rate constant for this reaction is ⩽ 1 × 10⁻²¹ cm³ molecule⁻¹ s⁻¹ at 298 K, consistent with recent environmental chamber data.     

SMX degradation by ozonation and UV radiation: a kinetic study

The rate constants of sulfamethoxazole (SMX) degradation by ozonation and UV₂₅₄ radiation were investigated under various parameters including influent ozone gas concentration, initial SMX concentration, UV light intensity, ionic strength, water quality in terms of varying anions (bicarbonate, sulfate and nitrate), humic acid (HA) and pH. The results indicated that the removal of SMX by ozonation and UV₂₅₄ radiation fitted well to a pseudo first-order kinetic model and the rate constants were in the range of (0.9-9.8) × 10⁻³ and (1.7-18.9) × 10⁻³ s⁻¹, respectively. The second-order rate constants of SMX with ozone (k_O3), under varying operational parameters, were also determined and varied in the range of (0.60-3.38) ± 0.13 × 10⁵ M⁻¹ s⁻¹. In addition, SMX degradation through UV pretreatment followed by ozonation in the presence of HA was proved to be an effective method which can remove SMX with a low ozone dose. The results suggested that ozonation of SMX was more affected by concentration of influent ozone gas, alkalinity, and HA, while incident UV light intensity, pH, and HA were the dominant factors influencing UV degradation of SMX.     

Selective removal of Cr(VI) from aqueous solution by adsorption on mangosteen peel

Mangosteen peel, rich in polyphenolic compounds, was used to prepare the adsorbent exhibiting highly selective adsorption for Cr(VI) over other metal ions such as Pb²⁺, Fe³⁺, Zn²⁺, Cd²⁺, and Cr³⁺ at the pH values of 1～4. The chemical modification method proposed by using calcium hydroxide is quite cost-effective and ecofriendly without using any toxic reagents or causing any secondary pollution. The adsorption isotherm results revealed that the adsorption of Cr(VI) on the gel fit well the Langmuir adsorption model, and the maximum adsorption capacity for Cr(VI) at pH levels 1, 2, 3, and 4 was evaluated to be 2.46, 2.44, 1.99, and 2.14 mol/kg, respectively. The adsorption mechanism for Cr(VI) on the saponified gel was verified to follow an esterifiaction reaction coupled with the reduction of Cr(VI) to Cr(III) in which H⁺ plays a role of promoter. Thus, modified mangosteen peel gel has the prominent selectivity and low cost for Cr(VI) removal.     

Wet-deposition fluxes of soluble chemical species and the elements in insoluble materials

From March to June 1996, eight rain events were collected by sequential sampling on time and volume basis in Kyoto University, Uji, Japan. Soluble chemical species Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Ca²⁺ and Mg²⁺ were measured by Ion Chromatography (IC); and the elements Si, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb in insoluble materials were measured by proton-induced X-ray emission (PIXE) technique. The wet-deposition flux of a soluble chemical species (or an element in insoluble materials) was calculated by the product of the chemical species (or the element) concentration and the corresponding rain intensity. The characteristics of sequential cumulative wet-deposition flux of the soluble chemical species and the elements in insoluble materials were examined. The factor controlling wet-deposition flux was discussed.     

Atmospheric concentrations and the deposition velocity to snow of nitric acid,sulfur dioxide and various particulate species

A study of deposition velocities to snow was conducted during the 1982–1983 and 1983–1984 winters at the University of Michigan Biological Station in northern Michigan. Weekly measurements were made of dry deposition rates to snow and the atmospheric concentrations of the depositing species. SO₂, with an average concentration of 2.2 ppb, was the dominant atmospheric sulfur containing species. NO₂, with an average concentration of 1.8 ppb, was the dominant atmospheric nitrogenous species. NO⁻₃ deposition was due primarily to HNO₃, which averaged 0.2 ppb. The HNO₃ deposition velocity averaged 1.4cm s⁻¹. The SO₂ deposition velocity varied with temperature, averaging 0.15 cm s⁻¹ for samples with appreciable exposure time above − 3°C, and 0.06 cm s⁻¹ for samples which remained below an ambient temperature of −3°C. Deposition velocities of Ca²⁺, Mg²⁺ , Na⁺, K⁺ and NH⁺₄ were 2.1, 1.5, 0.44, 0.51 and 0.10cm s⁻¹, respectively. The mass median diameters of these species were 4.4, 2.7, 1.8, 0.9 and 0.46 μm, respectively.     

Influence of NO2 and dissolved iron on the S(IV) oxidation in synthetic aqueous solution

The influence of dissolved NO₂ and iron on the oxidation rate of S(IV) species in the presence of dissolved oxygen is presented. To match the conditions in the real environment, the concentration of iron in the reaction solution and trace gases in the gas mixture was typical for a polluted atmosphere. The time dependence of HSO₃⁻, SO₄²⁻, NO₂⁻ and NO₃⁻ and the concentration ratio between Fe(II) and total dissolved iron were monitored. Sulphate formation was the most intensive in the presence of an SO₂/NO₂/air gas mixture and Fe(III) in solution. The highest contribution to the overall oxidation was from Fe-catalysed S(IV) autoxidation. The reaction rate in the presence of both components was equal to the sum of the reaction rates when NO₂ and Fe(III) were present separately, indicating that under selected experimental conditions there exist two systems: SO₂/NO₂/air and SO₂/NO₂/air/Fe(III), which are unlikely to interact with each other. The radical chain mechanism can be initiated via reactions Fe(III)–HSO₃⁻ and NO₂–SO₃²⁻/HSO₃⁻.