Spectroscopic studies and biological evaluation of some transition metal complexes of a novel Schiff base ligands derived from 5-arylazo-salicyladehyde and o-amino phenol

Synthesis and characterization of Cu(II), Ni(II), and Zn(II) Schiff bases complexes resulted from the condensation of salicylaldehyde derivatives with o-amino phenol were discussed using elemental analysis (carbon, hydrogen, and nitrogen), molar conductance, magnetic measurements, mass spectra, and electronic spectra. The essential bands of infrared, ¹HNMR, and UV-Vis spectra as well as thermogravimetric analysis corresponding to the active groups within the three ligands and their complexes were interpreted. The dehydration and decomposition processes of the [Cu(H₂L₁)(H₂O)](OAc)₂, [Ni(H₂L₁)(H₂O)]SO₄ · H₂O, [Zn(H₂L₁)(H₂O)]SO₄ · H₂O, [Cu(H₂L₂)(H₂O)](OAc)₂, [Ni(H₂L₂)(H₂O)]SO₄ · H₂O, [Zn(H₂L₂)(H₂O)]SO₄ · 2H₂O, [Cu(H₂L₃)(H₂O)](OAc)₂ · H₂O, [Ni(H₂L₃)(H₂O)]SO₄ · 2H₂O, [Zn(H₂L₃)(H₂O)]SO₄ complexes were studied thermodynamically using the integral method applying the Coats–Redfern and Horowitz–Metzger equations and the thermodynamic parameters were calculated. It was found from the elemental analysis and the thermal studies, that the ligand behaves as tridentate ligand forming chelates with 1 : 1 (metal : ligand) stoichiometrically. The molar conductance measurements of the complexes in dimethyl sulfoxide solvent indicate that the complexes have an electrolytic nature. The biological activities of the three ligands in comparison with metal(II) complexes were studied against different Gram positive and Gram negative bacteria.     

Copper recovery from waste printed circuit boards concentrated metal scraps by electrolysis

Copper recovery is the core of waste printed circuit boards (WPCBs) treatment. In this study, we proposed a feasible and efficient way to recover copper from WPCBs concentrated metal scraps by direct electrolysis and factors that affect copper recovery rate and purity, mainly CuSO₄·5H₂O concentration, NaCl concentration, H₂SO₄ concentration and current density, were discussed in detail. The results indicated that copper recovery rate increased first with the increase of CuSO₄·5H₂O, NaCl, H₂SO₄ and current density and then decreased with further increasing these conditions. NaCl, H₂SO₄ and current density also showed a similar impact on copper purity, which also increased first and then decreased. Copper purity increased with the increase of CuSO₄·5H₂O. When the concentration of CuSO₄·5H₂O, NaCl and H₂SO₄ was respectively 90, 40 and 118 g/L and current density was 80 mA/cm², copper recovery rate and purity was up to 97.32% and 99.86%, respectively. Thus, electrolysis proposes a feasible and prospective approach for waste printed circuit boards recycle, even for e-waste, though more researches are needed for industrial application.

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Hydrocarbons characterization in coastal sediments of the Argentine Patagonia using the nuclear magnetic resonance (NMR) spectroscopy

Hydrocarbons in Patagonian sediments were analyzed to evaluate their biogenic or petrogenic origins. Structural determination by ¹H-NMR spectrometry and principal component analysis (PCA) show that the first two principal components accounted for more than 75.7% of the variance. The results indicate that biogenic hydrocarbons have mainly linear hydrocarbon chains and polar groups (high H₂, H₄, H₅, and H_COOH), while petrogenic hydrocarbons show more branched chains and mainly mono-aromatic components, e.g., crude oil (high H₁, H_1A, and H₃) or mainly poly-aromatic components (high H₄, and H_2A) in weathering oil.     

A study on the landfill leachate and its impact on the groundwater quality of the greater area

Characterisation of the leachate originating from the Ano Liosia landfill (situated in Attica region, Greece) as well as assessment on the quality of the local aquifer were carried out. The experimental results showed that most of the parameters examined in the leachate samples such as colour, conductivity, TS, COD, NH₃–N, PO₄–P, SO₄ ^2–, Cl^–, K⁺, Fe and Pb were found in high levels. The organic load was quite high since the COD concentrations were in the range of 3250–6125mgL^–1. In addition, the low BOD/COD ratio (0.096–0.195), confirmed that the majority of this organic matter is not easily biodegradable. The groundwater near the landfill site was characterised as not potable and not suitable for irrigation water, since most of the physical and chemical parameters examined – such as colour, conductivity, DS, hardness, Cl^–, NH₃–N, COD, K⁺, Na⁺, Ca²⁺, Fe, Ni and Pb exceeded the permissible limits given by EE, EPA and the Greek Ministry of Agriculture. Furthermore, this study presents the application of the hydrologic evaluation of landfill performance (HELP) model for the determination of the yearly leakage from the base of the landfill after the final capping.     

The effects on human health and hydrogeochemical characteristics of the Kirkgeçit and Ozancik Hot Springs,Canakkale, Turkey

This investigation was carried out to determine the hydrogeochemical characteristics of the Kirkgeçit and Ozancik hot springs. The study areas are located northeast and southwest of the town of Çan, Çanakkale. During the investigation, geological maps of the hot springs and its surroundings were prepared, and hot waters and rock samples were collected from the study sites. The Paleogene–Neogene aged andesite, trachyandesite, andesitic tuff, silicified tuff and tuffites form the basement rocks in the Ozancik hot spring area. In the Kirkgeçit hot spring area, there are Lower Triassic aged mica and quartz schists at the basement rocks. The unit is covered by limestones and marbles of the same age. They are overlain by Quaternary alluvial deposits. A chemical analysis of the Kirkgeçit hot water indicates that it is rich in SO₄ ^2– (1200.2 mg L^–1), Cl^– (121.7 mg L^–1), HCO₃ ^– (32.5 mg L^–1), Na⁺ (494 mg L^–1), K⁺ (30.2 mg L^–1), Ca²⁺ (102 mg L^–1), Mg²⁺ (15.2 mg L^–1), and SiO₂ (65.22 mg L^–1). Chemical analysis of the Ozancik hot water indicates that it is rich in SO₄ ^2– (575 mg L^–1), Cl^– (193.2 mg L^–1), HCO₃ ^– (98.5 mg L^–1), Na⁺ (315 mg L^–1), K⁺(7.248 mg L^–1), Ca²⁺ (103 mg L^–1), Mg²⁺ (0.274 mg L^–1), and SiO₂(43.20 mg L^–1). The distribution of ions in the hot waters on the Schoeller diagram has an arrangement of r(Na⁺+K⁺)>rCa²⁺>rMg²⁺ and r(SO₄ ^2–)>rCl^–>r(HCO₃ ^–). In addition, the inclusion of Fe²⁺, Cu²⁺, Cr³⁺, Mn²⁺, Ni²⁺ and Hg²⁺ in the hot water samples indicates potential natural inorganic contamination. The water analysis carried out following the ICPMS-200 technique was evaluated according to the World Health Organisation and Turkish Standards. The use and the effects of the hot water on human health are also discussed in the paper.     

Air quality and micro-meterological monitoring of gaseous pollutants/flame emissions from burning crude petroleum in poultry house

Air quality of gaseous emissions from crude petroleum flames and fumes were monitored in a poultry house at 10 min intervals; from 10.10am–11.10am daily for 14 days. The crude petroleum burning was simulated in a metal burner, 22.86 cm high with a diameter of 17.80 cm and a thickness of 1.27 cm designed for the purpose. The micro-climate (ambient temperature, relative humidity and light intensity) of the experimental environment (poultry houses) was recorded. Results showed that the mean gaseous pollutants emitted before and during the experiments varied within the poultry house. Gases such as sulphur dioxide (SO₂), hydrogen sulphide (H₂S), methane(CH₄) and carbon monoxide (CO) were higher in the brooding than finishing phase, while volatile organic carbon (VOC) and suspended particulate matter (SPM) levels were lower at the brooding than finishing phase. The values obtained in this study for 60 min (at 10 min intervals) are far higher than the values elucidated by the Federal Environmental Protection Agency, which are outdoor air quality measurements as compared to those in this study measured indoors.     

Wet deposition chemistry studies at Suva, Fiji, a remote tropical island site in the south Pacific

A field project encompassing wet-only rainwater sampling was initiated as a bilateral Fiji/Australia activity. Normally, biweekly samples were collected, using a wet-only rainwater sampler, and analysed for H⁺, Na⁺, K⁺, Mg²⁺, NH₄ ⁺, Cl^–, NO₃ ^–, SO₄ ^2–, PO₄ ^3-, methane sulphonic acid, oxalic acid, formic acid and acetic acid. The pH of the rainwater ranged between 5.730 and 4.480 with an average value of 5.176, slightly lower than the pH of unpolluted rainwater saturated with atmospheric CO₂(pH = 5.650). Na⁺and Cl^–were the major ions with average concentrations of 98.15 M and 109.57 M respectively. There is an excellent correlation between the cation sum (average 147.71 eq L^-1) and the anion sum (average 142.12 eq L^-1) attesting to the quality of the data generated. This paper presents the detailed results of the study for a relatively clean remote island site in Suva, Fiji, latitude 18° 09 S, longitude 178° 27 E, height 6 m, and outlines prospects for further work.     

Improved methodology for ATP determination in marine environments

A simple technique is described for de-salting and concentrating adenosine triphosphate (ATP) extracted from seawater or marine sediment samples prior to assays with the standard luciferin-luciferase procedure. The technique involves chromatography of H₂SO₄ extracts on columns of activated carbon. The efficiency of ATP recovery from marine sediments using this pre-treatment was superior to that attained with either boiling Tris extraction or with H₂SO₄ extraction without subsequent purification. All ions which interfere with the luciferase reaction or precipitate ATP upon neutralization of acid extracts are removed with this procedure, thus eliminating the 50- to 100-fold dilutions required with other acid-extraction procedures. In addition, the purified ATP extracts may be concentrated up to 100-fold, thus greatly improving the sensitivity of ATP measurement in samples containing very low biomass. This procedure has been applied to ATP determination in marine sediments in the upwelling area off northwest Africa. The average ATP concentrations in the upper 6 cm of sediment from 1000 and 200 m were 195 and 545 ng per ml wet sediment, respectively.     

Evaluation of acidity in late Permian outcrop coals and its association with endemic fluorosis in the border area of Yunnan,Guizhou, and Sichuan in China

The junction area of Yunnan, Guizhou, and Sichuan provinces is the heaviest coal-burning endemic fluorosis zones in China. To better understand the pathogenicity of endemic fluorosis in this area, 87 coal samples from the late Permian outcrop or semi-outcrop coal seams were collected in eight counties of the junction area of Yunnan, Guizhou, and Sichuan provinces. The total fluorine and sulfate content, etc. in the coal was determined using combustion-hydrolysis/fluoride-ion-selective electrode method and ion chromatography, respectively. The results show that the total fluorine concentrations in the samples ranged from 44 to 382 µg g^?1, with an average of 127 µg g^?1. The average pH of the coals is 5.03 (1.86–8.62), and the sulfate content varied from 249 to 64,706 µg g^?1 (average 7127 µg g^?1). In addition, the coals were medium- and high-sulfur coals, with sulfur mass fraction ranging from 0.08 to 13.41%. By heating the outcrop coals, HF release from the coal was verified quantitatively without exception, while simulated combustion directly confirmed the release of sulfuric acid (H₂SO₄). The acid in coal may be in the form of acidic sulfate (\({\text{HSO}}_{4}^{ - }\)/H₂SO₄) because of a positive relationship between pH and \(p\left( {{\text{SO}}_{4}^{2 - } } \right)\) in the acidic coal. The possible reaction mechanism would be that a chemical reaction between the acid (H₂SO₄ or \({\text{HSO}}_{4}^{ - }\)) and fluorine in the coal occurred, thereby producing hydrogen fluoride (HF), which would be the chemical form of fluorine released from coal under relatively mild conditions. The unique chemical and physical property of HF may bring new insight into the pathogenic mechanism of coal-burning endemic fluorosis. The phenomenon of coal-burning fluorosis is not limited to the study area, but is common in southwest China and elsewhere. Further investigation is needed to determine whether other endemic fluorosis areas are affected by this phenomenon.     

Respiration rate and cost of swimming for Antarctic krill,<Emphasis Type="Italic"> Euphausia superba</Emphasis>, in large groups in the laboratory

Constructing realistic energy budgets for Antarctic krill, Euphausia superba, is hampered by the lack of data on the metabolic costs associated with swimming. In this study respiration rates and pleopod beating rates were measured at six current speeds. Pleopod beating rates increased linearly with current speed, reaching a maximum of 6 beats s^–1 at 17 cm s^–1. There was a concomitant linear increase in respiration rate, from 1.8 mg O₂ g_D^–1 h^–1 at 3 cm s^–1 to 8.0 mg O₂ g_D^–1 h^–1 at 17 cm s^–1. The size of the group tested (50, 100 and 300 krill) did not have a significant effect on pleopod beating rates or oxygen consumption (ANCOVA, F=0.264; P>0.05). The cost of transport reached a maximum of 75 J g^–1 km^–1 at 5 cm s^–1, and then decreased with increasing current speed to 29 J g^–1 km^–1. When considered in light of energy budgets for E. superba, these data indicate that the cost of swimming could account for up to 73% of total daily metabolic expenditure during early summer.Communicated by G.F. Humphrey, Sydney     

Assessment of groundwater contamination using geographic information systems

In this study two sites were selected in order to investigate groundwater contamination and spatial relationships among groundwater quality, topography, geology, landuse and pollution sources. One site is the Asan area, an agricultural district where pollution sources are scattered and which is mainly underlain by granite of Cretaceous age. The other site is the Gurogu area of Seoul city, an industrial district where an industrial complex and residential areas are located and which is mainly underlain by gneiss of Precambrian age. Groundwater samples collected from these districts were analysed for chemical constituents. An attribute value files of chemical constituents of groundwater and the spatial data layers were constructed and pollution properties were investigated to establish out spatial relationships between the groundwater constituents and pollution sources using geographic information systems (GIS).Relatively high contents of Si and HCO₃ ^– in the groundwater from the Asan area reflect the effect of water–rock interaction whereas high contents of Cl^–, NO₃ ^– and Ca²⁺ in the groundwater from the Gurogu area are due to the pollution of various sources. The significant seasonal variation of SiO₂, HCO₂ ^– and Ca²⁺ contents, and that of Ca²⁺ content were observed in the Asan and the Gurogu areas, respectively. Seasonal variation of pollutants such as Cl^–, NO₃ ^– and SO₄ ^2– was not observed in either area. Pollution over the critical level of the Korean drinking water standard has been investigated from 15 sampling sites out of 40 in the Asan area, and 33 sampling sites out of 51 in the Gurogu area. Pollution by NO₃ ^–, Cl^–, Fe²⁺, Mn²⁺, SO₄ ^2– and Zn²⁺ in the groundwater from the industrial district (Gurogu area) and that of NO₃ , SO₄ ^2– and Zn²⁺ in the groundwater from the agricultural district (Asan area) were observed. The principal pollutant in both areas is NO₃ ^–. Deep groundwater from the Asan area is not yet contaminated with NO₃ ^– except for one site, but most of the shallow groundwater site occurring near the potential point sources is seriously contaminated. From the result of buffering analysis, it seems clear that factories and stock farms are the principal pollution sources in the Asan area. The groundwater from the Gurogu area has already been seriously polluted considering the fact of NO₃ ^– contamination of deep groundwater. Chlorine pollution of shallow groundwater in the Gurogu area was also observed. Spatial relationship between pollution level and its source was clarified in this study by using GIS, which will be applicable to the effective management of groundwater quality.     

Movement and transformation of35S-labelled sulphate in the soil of a heavily polluted site in the Northern Czech Republic

Changes in chemistry and vertical distribution of³⁵S were investigated in column experiments using intact topsoil and repacked mineral soil horizons 1 to 20 weeks after tracer application (901 kBq³⁵S-SO₄ ^2– per column 6.5 cm in diameter). Horizons O, A, AE and Bvs of an Orthic Podzol were incubated at 20°C and wetted twice a week with 11 mm of natural throughfall precipitation (38.5 mg S0₄ ^2– L^–1-, pH 3.3). The top 35 cm of the soil contained 1,290 kg S ha^–1, or 18 times more than is the annual atmospheric S input (71.4 kg S ha^–1 yr^–1). Of this amount, 17.8 % was stored as inorganic sulphate S, 4.6 % as reduced inorganic S, and 77.6 % as organic S. In O + A and AE, free sulphate was the most abundant³⁵S form, while in Bvs the 35S activity of free and adsorbed sulphate was similar. The proportion of adsorbed sulphate increased with depth, averaging 23, 30 and 47 % of total inorganic sulphate³⁵S in O + A, AE and Bvs, respectively. Total specific activity of chemically transformed³⁵S (i.e., of reduced inorganic S and organic S) constituted 3.4, 3.8 and 105 % of inorganic sulphate³⁵S activity in O + A, AE and Bvs, respectively, in averaged weeks 2–4, and 7.5, 6.4 and 39.6 % in averaged weeks 11–13 in O+A, AE and Bvs, respectively. The turnover time of C-bonded³⁵S was shorter than that of ester sulphate³⁵S. An increase in FeS_2– ³⁵S with time indicated anaerobic conditions suitable for bacterial sulphate reduction. After 13 weeks, 68 % of the tracer was found deeper than 8 cm below soil surface.     

The chemistry of aluminum in the environment

There is increased concern over the effects of elevated concentrations of Al in the environment. Unfortunately, studies of the environmental chemistry and toxicity of Al have been limited by our understanding of the processes regulating the aqueous concentration, speciation and bioavailability of this element.Although Al is the most abundant metallic element in the Earth's crust, it is highly insoluble and generally unavailable to participate in biogeochemical reactions. However, under highly acidic or alkaline conditions, or in the presence of complexing ligands, elevated concentrations may be mobilized to the aquatic environment. Ecologically significant concentrations of Al have been reported in surface waters draining acid-sensitive regions that are receiving elevated inputs of acidic deposition. Acid- sensitive watersheds are characterized by limited release of basic cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) and/or retention of strong acid anions (SO₄ ^2–, NO₃ ^–, Cl^–). Under these conditions inputs of strong acids are not completely neutralized, but rather acidic water is exported from the terrestrial environment. It has been hypothesized that acidic deposition to acid-sensitive watersheds mobilizes Al within the mineral soil, causing elevated concentrations in soil solutions and surface waters. As a result of mineral phase solubility constraints, concentrations of aqueous Al increase exponentially with decreases in pH below 6.0.Monomeric Al occurs as a series of complexes in the aqueous environment, including aquo, OH^–, F^–, SO₄ ^2–, HCO₃ ^– and organic species. Of these aquo, OH^–, F^– and organic complexes are the most significant in natural waters.Elevated concentrations of Al are ecologically significant because: 1) Al is an important pH buffer in acidic waters, regulating the lower limit of pH values following acidification by strong acids; 2) through adsorption and coagulation reactions, Al may alter the cycling and availability of important elements like phosphorus, organic carbon and certain trace metals; 3) Al may serve as a coagulant facilitating the removal of light attenuating materials, thereby increasing the clarity and decreasing the thermal stability of lakes; and 4) Al is potentially toxic to organisms. Better understanding of the chemistry and speciation of Al is essential to assess these effects.     

The influence of macrofauna on estuarine benthic community metabolism: a microcosm study

Effects of benthic macrofauna (Corophium volutator, Hydrobia sp., Nereis virens) on benthic community metabolism were studied over a 65-d period in microcosms kept in either light/dark cycle (L/D-system) or in continuous darkness (D-system). Sediment and animals were collected in January 1986 in the shallow mesohaline estuary, Norsminde Fjord, Denmark. The primary production in the L/D-system after 10 d acted as a stabilizing agent on the O₂ and CO₂ flux rates, whereas the D-system showed decreasing O₂ and CO₂ flux throughout the period. Mean O₂ uptake over the experimental period ranged from 0.38 to 1.24 mmol m^–2 h^–1 and CO₂ release varied from 0.80 to 1.63 mmol m^–2 h^–1 in both systems. The presence of macrofauna stimulated community respiration rates measured in darknes, 1.4 to 3.0 and 0.9 to 2.0 times for O₂ and CO₂, respectively. In contrast, macrofauna lowered primary production. Gross primary production varied from 1.06 to 2.26 mmol O₂ m^–2 h^–1 and from 1.26 to 2.62 mmol CO₂ m^–2 h^–1. The community respiratory quotient (CRQ, CO₂/O₂) was generally higher in the begining of the experiment (0–20 d, mean 1.89) than in the period from Days 20 to 65 (mean 1.38). The L/D-system exhibited lower CRQ (ca. 1) than the D-system. The community photosynthetic quotient varied for both net and gross primary production from 0.64 to 1.03, mean 0.81. The heterotrophic D-system revealed a sharp decrease in the sediment content of chlorophyll a as compared to the initial content. In the autotrophic L/D-system, a significant increase in chlorophyll a concentration was observed in cores lacking animals and cores with C. volutator (The latter species died during the experiment). Due to grazing and other macrofauna activities other cores of the L/D-system exhibited no significant change in chlorophyll a concentration. Community primary production was linearly correlated to the chlorophyll a content in the 0 to 0.5 cm layer. Fluxes of DIN (NH₄ ⁺+NO₂ ^–+NO₃ ^–) did not reveal significant temporal changes during the experiment. Highest rates were found for the cores containing animals, mainly because of an increased NH₄ ⁺ flux. The release of DIN decreased significantly due to uptake by benthic microalgae in the L/D-system. No effects of the added macrofauna were found on particulate organic carbon (POC), particulate organic nitrogen (PON), total carbon dioxide (TCO₂) and NH₄ ⁺ in the sediment. The ratio between POC and PON was nearly constant (9.69) in all sediment dephts. The relationship between TCO₂ and NH₄ ⁺ was more complex, with ratios below 2 cm depth similar to those for POC/PON, but with low ratios (3.46) at the sediment surface.     

Removal of Cr(VI) from aqueous solutions by the culm of bamboo grass treated with concentrated sulfuric acid

We prepared a carbonaceous sorbent for Cr(VI) from the culm of Sasa kurilensis by dehydration with concentrated H₂SO₄. The removal of Cr(VI) by the sorbent was highly solution pH dependent and mainly governed by physicochemical sorption. The equilibrium data fit well in the Langmuir isotherm model and indicate the endothermic nature of the Cr(VI) sorption. The desorption experiments suggest that the Cr(VI) sorption is generally irreversible, owing to strong interaction of HCrO₄⁻ with the active sites of the sorbent.     

Automatic potentiometric determination of dissolved oxygen

Commercially available automatic titration systems were tested in 1988 for potentiometric titration of liberated iodine by the Winkler method of oxygen determination. The potentiometric equivalence point was also compared to the manual starch end point. Finally the automatic method was used in order to estimate belowhalocline respiration in the Kattegat, Sweden. Standard deviations of 0.007 ml O₂ l^–1 or 0.1 to 0.3% coefficients of variation (% standard deviation of the mean) were achieved when titrating 25 ml from replicate 60-ml oxygen bottles using the automatic method, or 50 ml manually. The precision for replicate titrations of 50-ml aliquots of 0.001N KIO₃ was <0.05% (0.002 ml 0.01N Na₂S₂O₃) for the automatic method. Titration time for 25-ml aliquots was 2 to 4 min, somewhat longer than for manual titrations (1 to 1.5 min). However, during titration the operator is free to perform other tasks. It is not possible to use automatic sample changers, due to rapid iodine volatilization. The equipment can be handled by relatively unskilled analysts and is suitable for use on board research vessels or in field stations [weight for a Mettler^TM titrator (Mettler Instrumente AG, Greifensee, Switzerland) <10 kg, volume <0.1 m³]. Below-halocline oxygen consumption in the SE Kattegat ranged from 0 to 6 ml O₂ m^–3 h^–1 (mean values for September and October 1988=1.69 and 0.66 ml O₂ m^–3 h^–1, respectively, with 95% confidence limits of ca. ±0.6 ml O₂ m^–3 h^–1).     

Removal of elemental mercury by KI-impregnated clay

This study described the use of clay impregnated by KI in gas phase elemental mercury (Hg^o) removal in flue gas. The effects of KI loading, temperature, O₂, SO₂ and H₂O on Hg^o removal were investigated using a fixed bed reactor. The Hg^o removal efficiency of KI-clay with 3% KI loading could maintain at a high level (approximately 80 %) after 3 h. The KI-clay demonstrated to be a potential adsorbent for Hg^o removal when compared with activated carbon based adsorbent. O₂ was found to be an important factor in improving the Hg^o removal. O₂ was demonstrated to assist the transfer of KI to I₂ on the surface of KI-clay, which could react with Hg^o directly. NO and SO₂ could slightly improve Hg^o removal, while H₂O inhibited it greatly. The results indicated that after adsorption, most of the mercury escaped from the surface again. Some of the mercury may have been oxidized as it left the surface. The results demonstrated that the chemical reaction primarily occurred between KI and mercury on the surface of the KI-clay.     

Atmospheric Sulfur Deposition onto Different Ecosystems Over China

The regional acid deposition model system (RegADMS) was applied to simulate the air sulfur deposition onto different landuse types over China, in which the dry deposition velocities of SO₂ and sulfate aerosol (SO ₄ ^2– ) were estimated by use of a big leaf resistance analogy model and the wet scavenging coefficients were parameterized in terms of precipitation rate. Investigations show that the annual total sulfur deposition over mainland China is 7.24 mt (1 mt = 10⁶ ton) , in which dry deposition and wet deposition accounts for 56 and 44%, respectively. The sulfur deposition onto agriculture land, grass land, and forest land is 1.09, 3.6 and 1.41 mt, respectively, which sums 6.1 mt and accounts for 84% of the total sulfur deposition. The modeled sulfur deposition was in agreement with the measurement conducted at farmland in Yingtan, a typical read soil region in Jiangxi province of China, during the period of November 1998–October 1999. The total sulfur deposition at the Yingtan site is about 10.3 gm^–2 year^–1 of which 83% is dry deposition. The modeling sulfur deposition at the same site is 8.4 gm^–2 year^–1. Furthermore, the comparison between RegADMS and RAINS-ASIA on modeling regional sulfur deposition shows the consistence of the two models. The correlation coefficient between the simulated sulfur deposition at the medium-large cities reaches 0.72.     

Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

Improving simulations of sulfate aerosols during winter haze over Northern China: the impacts of heterogeneous oxidation by NO<Subscript>2</Subscript>

We implemented the online coupled WRF-Chem model to reproduce the 2013 January haze event in North China, and evaluated simulated meteorological and chemical fields using multiple observations. The comparisons suggest that temperature and relative humidity (RH) were simulated well (mean biases are–0.2K and 2.7%, respectively), but wind speeds were overestimated (mean bias is 0.5 m?s^–1). At the Beijing station, sulfur dioxide (SO₂) concentrations were overpredicted and sulfate concentrations were largely underpredicted, which may result from uncertainties in SO₂ emissions and missing heterogeneous oxidation in current model. We conducted three parallel experiments to examine the impacts of doubling SO₂ emissions and incorporating heterogeneous oxidation of dissolved SO₂ by nitrogen dioxide (NO₂) on sulfate formation during winter haze. The results suggest that doubling SO₂ emissions do not significantly affect sulfate concentrations, but adding heterogeneous oxidation of dissolved SO₂ by NO₂ substantially improve simulations of sulfate and other inorganic aerosols. Although the enhanced SO₂ to sulfate conversion in the HetS (heterogeneous oxidation by NO₂) case reduces SO₂ concentrations, it is still largely overestimated by the model, indicating the overestimations of SO₂ concentrations in the North China Plain (NCP) are mostly due to errors in SO₂ emission inventory.

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