Oxidative transformations of environmental pharmaceuticals by Cl₂, ClO₂, O₃, and Fe(VI): kinetics assessment

Several pharmaceuticals have been detected globally in surface water and drinking water, which indicate their insufficient removal from water and wastewater using conventional treatment methods. This paper reviews the kinetics of oxidative transformations of pharmaceuticals (antibiotics, lipid regulators, antipyretics, anticonvulsants, and beta-blockers) by Cl(2), ClO(2), O(3), and ferrate(VI) (Fe(VI)O(4)(2-),Fe(VI)) under treatment conditions. In the chlorination of sulfonamide antibiotics, HOCl is the major reactive Cl(2) species whereas in the oxidation by Fe(VI), HFeO(4)(-) is the dominant reactive species. Both oxidation processes can oxidize sulfonamides in seconds at a neutral pH (t(1/2)≤ 220 s; 1 mg L(-1) HOCl or K(2)FeO(4)). The reactivity of O(3) with pharmaceuticals is generally higher than that of HOCl (k(app,pH 7) (O(3))=1-10(7)M(-1)s(-1); k(app,pH 7) (HOCl)=10(-2)-10(5)M(-1)s(-1)). Ozone selectively oxidizes pharmaceuticals and reacts mainly with activated aromatic systems and non-protonated amines. Oxidative transformation of most pharmaceuticals by O(3) occurs in seconds (t(1/2)≤ 100 s; 1 mg L(-1) O(3)) while half-lives for oxidations by HOCl differ by at least two orders of magnitude. Ozone appears to be efficient in oxidizing pharmaceuticals in aquatic environments. The limited work on Fe(VI) shows that it can also potentially transform pharmaceuticals in treatment processes.     

Photocatalytic oxidation of NOx using composite sheets containing TiO2 and a metal compound

The photocatalytic oxidation of nitrogen oxides (NO(x)) over titanium dioxide (TiO(2)) sheets containing metal compounds (MCs) had been studied. Calcium oxide (CaO), magnesium oxide (MgO), calcium carbonate (CaCO(3)), aluminium oxide (Al(2)O(3)) and ferric oxide (Fe(2)O(3)) were used as MCs. Al(2)O(3) and Fe(2)O(3) added to the TiO(2) sheet did not affect the photooxidation of nitrogen oxides (NO(x)). The CaO sheet treated with TiO(2) sol had the greatest efficiency as a NO(x) remover under UV irradiation. It is believed that CaO has a high adsorptivity for nitrogen dioxide (NO(2)) and nitric acid (HNO(3)). The amount of NO(x) removed by a TiO(2) sheet including MC showed a tendency to increase with increasing pH of the MC suspension, i.e. there is a good correlation between the alkalinity of the MC and the retention of NO(2) and HNO(3).     

Kinetics and mechanism of nitrite oxidation by hypochlorous acid in the aqueous phase

The rate coefficient for the reaction of nitrite with hypochlorite and hypochlorous acid has been studied using spectrophotometric measurements. The reaction rate has been determined in a wide range of H(+) concentration (5< or =-log[H(+)]< or =11). The kinetics were carried out as a function of NO(2)(-), H(+) and total hypochlorite ([HOCl](total)=[HOCl]+[ClO(-)]+[ClNO(2)]) concentrations. The observed overall rate law is described by: -d[HClO](T)dt=[a[NO(2)(-)](2)+b[NO(2)(-)]][H(+)](2)c+d[H(+)]+e[NO(2)(-)][H(+)](2)[HOCl](total)At T=298 K and in Na(2)SO(4) at an ionic strength (I=1.00 M), we obtained using a nonlinear fitting procedure: a=(1.83+/-0.36)x10(7) s(-1), b=(1.14+/-0.23)x10(5) Ms(-1), c=(1.12+/-0.17)x10(-13) M, d=(1.43+/-0.29)x10(-6) M(2) and e=(1.41+/-0.28)x10(3) M where the errors represent 2sigma. According to the overall rate law, a/b=k(1)/k(3), b/e=k(3), c=K(w), d/c=K(a), d=K(a)K(w) and e=K(1)K(a). In Na(2)SO(4) at an ionic strength (I=1.00 M), the values of K(1) and K(a) are (1.1+/-0.1)x10(-4) and 1.28x10(7) M(-1), respectively. A mechanism is proposed for the NO(2)(-) oxidation which involves the reversible initial step: NO(2)(-)+HOCl left harpoon over right harpoon ClNO(2)+OH(-) (K(1)), while ClNO(2) undergoes the two parallel reactions: attack by NO(2)(-) (k(1)) and hydrolysis (k(3)). ClNO(2) and N(2)O(4) are proposed as important intermediates as they control the mechanism. The rate coefficients k(1) and k(3) have been determined at different ionic strengths in NaCl and Na(2)SO(4). The influence of the ionic strength and ionic environment has been studied in this work.     

Acceleration of catalase and peroxidase activities in Lemna minor L. and Allium cepa L. in response to low levels of aquatic mercury

The purpose of this study was to assess certain physiological responses of Lemna minor L. (duckweed) and Allium cepa L. (onion) to aquatic mercury at low concentrations. Following a 96-h exposure of plants to nutrient medium contaminated with known levels of mercuric chloride (HgCl(2)), 0.001 to 4 mg litre(-1) (0.0007 to 2.95 mg Hg litre(-1)) or methyl mercuric chloride (MeHgCl(2)), 0.0001 to 0.1 mg litre(-1) (0.0007 to 0.07 mg Hg litre(-1)), the physiological endpoints measured were the growth of fronds (Lemna minor) or roots (Allium cepa), and catalase and peroxidase activities in both plant assays. The EC(50) for HgCl(2) on the basis of the growth curve of Lemna minor was found to be 2.1 mg litre(-1). HgCl(2) and MeHgCl(2) were lethal to L. minor at concentrations of 4 and 0.01 mg litre(-1), respectively. The range of low concentrations that accelerated growth as well as enzymic activities in L. minor was 0.004 to 0.04 mg litre(-1) for HgCl(2) and 0.001 mg litre(-1) for MeHgCl(2). HgCl(2) and MeHgCl(2) induced maximum enzymic activity in Lemna fronds at concentrations of 0.008 and 0.0005 mg litre(-1), respectively. In Allium roots, catalase activity was accelerated at all the concentrations of HgCl(2) (0.001-2 mg litre(-1)) and MeHgCl(2) (0.0001-0.1 mg litre(-1)) tested. The activity of peroxidase was, however, accelerated by HgCl(2) at concentration range 0.01-1.0 mg litre(-1), or by MeHgCl(2) at 0.001 mg litre(-1). The concentrations of HgCl(2) and MeHgCl(2) that induced the highest enzymic activity in Allium roots were 0.05 mg litre(-1) and 0.001 mg litre(-1), respectively.     

Assessment of the bioavailability of rare earth elements in soils by chemical fractionation and multiple regression analysis

The bioavailability of rare earth elements (REEs) in soils was evaluated, based on the combination of chemical fractionation and multiple regression analysis. REEs in soils were partitioned by a sequential extraction procedure into water soluble (F(ws)), exchangeable (F(ec)), bound to carbonates (F(cb)), bound to organic matter (F(om)), bound to Fe-Mn oxides (F(fm)) and residual (F(rd)) fractions. Alfalfa (Medicago Staiva Linn.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 35 days. The concentrations of REEs in fractions and plant were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Chemical fractionation showed that (F(ws)) fraction of REEs was less than 0.1% and residual (F(rd)) was the dominant form, more than 60% in soils. Bioaccumulation of REEs was observed in Alfalfa. REE availability to the plant was evaluated by multiple regression analysis. F(ws), F(ec), F(cb) and F(om) fractions were significantly correlated with REE uptake by alfalfa. But the exchangeable Pr(F(ec)) was significantly correlated with Pr concentration in alfalfa. F(ec), F(cb) and F(om) greatly contributed to La and Nd bioavailability; F(ec) and F(om) to Ce, Gd and Dy; F(ec) and F(cb) to Yb; and F(ws), F(ec) and F(om) to total REEs. This meant that the bioavailability of different species of REEs varied with individual REE. The results of this study indicated that the sequential extraction procedure, in conjunction with multiple regression analysis, may be useful for the prediction of plant uptake of REEs from soils.     

Effects of experimental parameters on NF(3) decomposition fraction in an oxygen-based RF plasma environment

Clean procedure is one of the major emitters of perfluorinated compounds (PFCs) in semiconductor manufacturing. Nitrogen trifluoride (NF(3)) is increasingly the process gas of choice for eliminating PFC emissions. However, its toxic to human and similar global warming potential compared to most other PFCs made NF(3) warranted much more investigation. This study demonstrated a radio-frequency plasma system for decomposing NF(3). The effects of experimental parameters: input power, O(2)/NF(3) ratio, operational pressure and NF(3) feeding concentration on NF(3) decomposition fraction (eta(NF3)) and energy efficiency E(NF3) were examined in detail. The analytical results demonstrated that the NF(3) was almost completely decomposed (>99%) at input power=30W, [NF(3)](in)=1.0% and eta(NF3) increased with input power. However, adding O(2) to the system inhibited NF(3) decomposition and decreased E(NF3). Moreover, eta(NF3) and E(NF3), decreased with gradually increasing operational pressure. Notably, increasing the NF(3) feeding concentration increased molecule density, reducing eta(NF3), but increasing E(NF3). Furthermore, the products detected in the NF(3)/O(2)/Ar plasma system were NO(2), NO, N(2)O, SiF(4), N(2) and F(2). Potential reaction pathways in the oxygen-based NF(3) plasma environment were built-up and elucidated.     

Reduction of ferrate(VI) and oxidation of cyanate in a Fe(VI)-TiO2-UV-NCO- system

The aqueous photocatalytic degradation of cyanate (NCO(-)), which is a long-lived neurotoxin formed during the remediation of cyanide in industrial waste streams, was studied in the ferrate(VI)-UV-TiO2-NCO(-) system. Kinetics measurements of the photocatalytic reduction of ferrate(VI) were carried out as a function of [NCO(-)], [ferrate(VI)], [O(2)], light intensity (I(o)), and amount of TiO2 in suspensions at pH 9.0. The photocatalytic reduction rate of ferrate(VI) in the studied system can be expressed as -d[Fe(VI)]/dt=kI(o)(0.5) [NCO(-)] [TiO2]. The rate of photocatalytic oxidation of cyanate with ferrate(VI) was greater than the rate in the analogous system without ferrate(VI). The possibility of involvement of reactive ferrate(V) species for this enhancement was determined by studying the reactivity of ferrate(V) with NCO(-) in a homogeneous solution using a premix pulse radiolysis technique. The rate constant for the reaction of ferrate(V) and NCO(-) in alkaline medium was estimated to be (9.60+/-0.07) x 10(2) M(-1) s(-1), which is much slower than the ferrate(VI) self-decomposition reaction (k approximately 10(7) M(-1) s(-1)). An analysis of the kinetic data in the Fe(VI)-UV-TiO2-NCO(-) system suggests that ferrate(V) is not directly participating in the oxidation of cyanate. Possible reactions in the system are presented to explain results of ferrate(VI) reduction and oxidation of cyanate.     

Algal toxicity of antibacterial agents used in intensive farming

The growth inhibiting effects of eight antibiotics used either therapeutically or as growth promoters in intensive farming on two species of micro algae, Microcystis aeruginosa (freshwater cyanobacteria) and Selenastrum capricornutum (green algae) were investigated. The effects of the antibiotics benzylpenicillin (penicillin G) (BP), chlortetracycline (CTC), olaquindox (O), spiramycin (SP), streptomycin (ST), tetracycline (TC), tiamulin (TI) and tylosin (TY) were tested in accordance with the ISO 8692 (1989) standard protocol. Algal growth was measured as increase in chlorophyll concentration by extraction with ethanol followed by measurement of fluorescence. Results were quantified in terms of growth rates using the Weibull equation to describe the concentration response relationship. The toxicity (EC50 value, mg/l) in alphabetic order were BP (0.006); CTC (0.05); O (5.1); SP (0.005); ST (0.007); TC (0.09); TI (0.003) and TY (0.034) for M. aeruginosa. BP (NOEC = 100); CTC (3.1); O (40); SP (2.3); ST (0.133); TC (2.2); TI (0.165) and TY (1.38) for S. capricornutum. In this investigation M. aeruginosa is found to be about two orders of magnitude more sensitive than S. capricornutum. It was observed that most of the compounds were unstable during the test period due to hydrolysis and photolysis.     

Fluxes of oxidised and reduced nitrogen above a mixed coniferous forest exposed to various nitrogen emission sources

Concentrations of nitrogen gases (NH(3), NO(2), NO, HONO and HNO(3)) and particles (pNH(4) and pNO(3)) were measured over a mixed coniferous forest impacted by high nitrogen loads. Nitrogen dioxide (NO(2)) represented the main nitrogen form, followed by nitric oxide (NO) and ammonia (NH(3)). A combination of gradient method (NH(3) and NO(x)) and resistance modelling techniques (HNO(3), HONO, pNH(4) and pNO(3)) was used to calculate dry deposition of nitrogen compounds. Net flux of NH(3) amounted to -64 ng N m(-2) s(-1) over the measuring period. Net fluxes of NO(x) were upward (8.5 ng N m(-2) s(-1)) with highest emission in the morning. Fluxes of other gases or aerosols substantially contributed to dry deposition. Total nitrogen deposition was estimated at -48 kg N ha(-1) yr(-1) and consisted for almost 80% of NH(x). Comparison of throughfall nitrogen with total deposition suggested substantial uptake of reduced N (+/-15 kg N ha(-1) yr(-1)) within the canopy.     

Identification of highly brominated analogues of Q1 in marine mammals

Three novel halogenated organic compounds (HOCs) have been identified in the blubber of marine mammals from coastal New England with the molecular formulae C(9)H(3)N(2)Br(6)Cl, C(9)H(3)N(2)Br(7), and C(9)H(4)N(2)Br(5)Cl. They were identified using high and low resolution gas chromatography mass spectrometry (GCMS) and appear to be highly brominated analogues of Q1, a heptachlorinated HOC suspected to be naturally produced. These compounds were found in Atlantic white sided dolphin (Lagenorhynchus acutus), bottlenose dolphin (Tursiops truncatus), common dolphin (Delphinus delphis), Risso's dolphin (Grampus griseus), harbor porpoise (Phocoena phocoena), beluga whale (Delphinapterus leucas), fin whale (Balaenoptera physalus), grey seal (Halichoerus grypus), harp seal (Phoca groenlandica) and a potential food source (Loligo pealei) with concentrations as high as 2.7 microg/g (lipid weight). The regiospecificity of C(9)H(3)N(2)Br(6)Cl is suggestive of a biogenic origin. Debromination of C(9)H(3)N(2)Br(6)Cl may be significant in the formation of C(9)H(4)N(2)Br(5)Cl.     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Simulation modeling for nitrogen removal and experimental estimation of mass fractions of microbial groups in single-sludge system

Nitrification-denitrification in a single-sludge nitrogen removal system (SSNRS; with a sufficient carbon source for denitrification) was performed. With an increase in the mixed liquor recycle ratio (R(m)) from 1 to 2, the total nitrogen (TN) removal efficiency at a lower volumetric loading rate (VLR=0.21 NH(4)(+)-N m(-3) d(-1)) increased, but the TN removal efficiency at a higher VLR (0.35 kg NH(4)(+)-N m(-3) d(-1)) decreased. A kinetic model that accounts for the mass fractions of Nitrosomonas, Nitrobacter, nitrate reducer and nitrite reducer (f(n1), f(n2), f(dn1), and f(dn2)) in the SSNRS and an experimental approach for the estimation of the mass fractions of nitrogen-related microbial groups are also proposed. The estimated f(dn1) plus f(dn2) (0.65-0.83) was significantly larger than the f(n1) plus f(n2) (0.28-0.32); the f(n1) (0.21-0.26) was larger than the f(n2) (0.05-0.07); and the f(dn1) (0.32-0.45) varied slightly with the f(dn2) (0.33-0.38). At the lower VLR, the f(dn1) plus f(dn2) increased with increasing R(m); however at the higher VLR, the f(dn1) plus f(dn2) did not increase with increasing R(m). By using the kinetic model, the calculated residual NH(4)(+)-N and NO(2)(-)-N in the anoxic reactor and NO(2)(-)-N and NO(3)(-)-N in the aerobic reactor were in fairly good agreement with the experimental data; the calculated NO(3)(-)-N in the anoxic reactor was over-estimated and the calculated NH(4)(+)-N in the aerobic reactor was under-estimated.     

Effects of pre-exposure to ultraviolet-B radiation on responses of tomato (Lycopersicon esculentum cv. New Yorker) to ozone in ambient and elevated carbon dioxide

Patterns of environmental change in the biosphere include concurrent and sequential combinations of increasing ultraviolet (UV-B) and ozone (O(3)) at increasing carbon dioxide (CO(2)) levels; long-term changes are resulting mainly from stratospheric O(3) depletion, greater tropospheric O(3) photochemical synthesis, and increasing CO(2) emissions. Effects of selected combinations were evaluated in tomato (Lycopersicon esculentum cv. New Yorker) seedlings using sequential exposures to enhanced UV-B radiation and O(3) in differential CO(2) concentrations. Ambient (7.2 kJ m(-2 )day(-1)) or enhanced (13.1 kJ m(-2) day(-1)) UV-B fluences and ambient (380 microl l(-1)) or elevated (600 microl l(-1)) CO(2) were imposed for 19 days before exposure to 3-day simulated O(3) episodes with peak concentrations of 0.00, 0.08, 0.16 or 0.24 microl l(-1) O(3) in ambient or elevated CO(2). CO(2) enrichment increased dry mass, leaf area, specific leaf weight, chlorophyll concentration and UV-absorbing compounds per unit leaf area. Exposure to enhanced UV-B increased leaf chlorophyll and UV-absorbing compounds but decreased leaf area and root/shoot ratio. O(3) exposure generally inhibited growth and leaf photosynthesis and did not affect UV-absorbing compounds. The highest dose of O(3) eliminated the stimulating effect of CO(2) enrichment after ambient UV-B pre-exposure on leaf photosynthesis. Pre-exposure to enhanced UV-B mitigated O(3) damage to leaf photosynthesis at elevated CO(2).     

Removing and recovering gas-phase elemental mercury by Cu(x)Co(3-x)O(4) (0.75< or = x < or =2.25) in the presence of sulphur compounds

The Hg(0) oxidation ability and reusability of Cu(x)Co(3-x)O(4) were investigated in an attempt to improve SO(2) anti-poisoning ability of metal oxide and produce more economic and effective sorbents for the control of Hg(0) emission from combustion processes. The influence of copper content on Cu(x)Co(3-x)O(4)'s (0.75< or = x < or =2.25) oxidation ability of Hg(0) in the presence of SO(2) was investigated. According to the X-ray diffraction, Brunauer-Emmett-Teller (BET) and mass balance analysis on mercury, we found that Cu(1.5)Co(1.5)O(4) showed the highest S(BET) and best Hg(0) oxidation ability. With continuous increase of x from 0.75 to 2.25, Cu(x)Co(3-x)O(4)'s SO(2) anti-poisoning ability increased. The analysis results of the X-ray photoelectron spectroscopy manifested that the adsorptive mercury species on spent Cu(1.5)Co(1.5)O(4) was HgO. The spent Cu(1.5)Co(1.5)O(4) could be regenerated by thermal decomposition at 673K and regenerated Cu(1.5)Co(1.5)O(4) showed higher Hg(0) oxidation ability due to Hg-doping. Regenerated enrichment Hg(0) was collected using activated carbon at an ambient temperature to eliminate the secondary pollution.     

Analysis of serpentinophytes from north-east of Portugal for trace metal accumulation--relevance to the management of mine environment

In north–east of Portugal, the serpentinized area is about 8000 ha with a characteristic geology and flora. The serpentine plant community and respective soils were analyzed to examine the trace metal budget in different tissues of the plants exhibiting resistance to trace metals. One hundred and thirty five plant species belonging to 39 families and respective soils have been analyzed for total Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. Substantial amounts of Ni, Cr, Co and Mn were detected in plant tissues which are listed below: Ni: Alyssum serpyllifolium (38 105); Bromus hordeaceus (1467); Linaria spartea (492); Plantago radicata (140); Lavandula stoechas (118) and Cistus salvifolius (114); Cr: L. spartea (706.7); Ulmus procera (173.4); A. serpyllifolium (129.3); Cistus ladanifer (40.8); L. stoechas (29.5); P. radicata (27.81); Setariopsis verticillata (25.7); Plantago lanceolata (24); Digitalis purpurea (23.4); Logfia minima (23.1); Arenaria querioides (23); Hieracium peleteranum (22.7); Arenaria montana (14.5); Co: A. serpyllifolium (145.1); L. spartea (63.2); P. radicata (10.4); H. peleteranum (7.3); Lepidium heterophyllum (6.9); A. querioides (6.6); C. salvifolius (6.5); C. ladanifer (6.3); L. stoechas (6.1); Anthyllis lotoides (6.1); L. minima (6.1); Euphorbia falcata (5.7) and B. hordeaceus (5.6); Mn: A. serpyllifolium (830); L. spartea (339); L. stoechas (187.1); L. minima (182.7); Castanea sativa (125); Spergula pentandra (124); P. radicata (119); Cytisus striatus (115.4); Quercus pyrenaica (110); Teucrium scorodonia (109.4); Fraxinus vulgaris (109); Anthyllis sampaiana (108); Quercus ilex (108). The significance of serpentine flora, need for conservation of these fragile and environmentally invaluable plant resources for possible use for in situ remediation of metalliferous substrates are presented in this paper.     

Investigation of heavy metal accumulation in Polygonum thunbergii for phytoextraction

In this study, cadmium (II), lead (II), copper (II) and zinc (II) were determined in Polygonum thunbergii and soil from the Mankyung River watershed, Korea. Soil samples contained detectable lead (<17.5 g g(-1)), copper (<8.4 g g(-1)) and zinc (<24.5 g g(-1)), whereas cadmium was undetectable. Whole plants of P. thunbergii contained detectable lead (<320.8 g g(-1)), copper (<863.2 g g(-1)) and zinc (<2427.3 g g(-1)), whereas cadmium was detectable only in the stem (<7.4 g g(-1)) and root (<10.1 g g(-1)). Whole plant concentrations were very different for each metal, particularly in the case of zinc. The mean content of heavy metal in the whole plants increased in the order of cadmium (8.5 g g(-1))相似文献   

Interactive effects of ozone and elevated carbon dioxide on the growth and physiology of black cherry, green ash, and yellow-poplar seedlings

Potted seedlings of black cherry (Prunus serotina Ehrh.) (BC), green ash (Fraxinus pennsylvanica Marsh.) (GA), and yellow-poplar (Liriodendron tulipifera L.) (YP) were exposed to one of the four treatments: (1) charcoal-filtered air (CF) at ambient CO(2) (control); (2) twice ambient O(3) (2 x O(3)); (3) twice ambient CO(2) (650 microl l(-1)) plus CF air (2 x CO(2)); or (4) twice ambient CO(2) (650 microl l(-1)) plus twice ambient O(3) (2 x CO(2) + 2 x O(3)). The treatments were duplicated in eight continuously stirred tank reactors for 10 weeks. Gas exchange was measured during the last 3 weeks of treatment and all seedlings were destructively harvested after 10 weeks. Significant interactive effects of O(3) and CO(2) on the gas exchange of all three species were limited. The effects of elevated CO(2) and O(3), singly and combined, on light-saturated net photosynthesis (A(max)) and stomatal conductance (g(s)) were inconsistent across species. In all three species, elevated O(3) had no effect on g(s). Elevated CO(2) significantly increased A(max) in GA and YP foliage, and decreased g(s) in YP foliage. Maximum carbon exchange rates and quantum efficiencies derived from light-response curves increased, while compensation irradiance and dark respiration decreased in all three species when exposed to 2 x CO(2). Elevated O(3) affected few of these parameters but any change that was observed was opposite to that from exposure to 2 x CO(2)-air. Interactive effects of CO(2) and O(3) on light-response parameters were limited. Carboxylation efficiencies, derived from CO(2)-response curves (A/C(i) curves) decreased only in YP foliage exposed to 2 x CO(2)-air. In general, growth was significantly stimulated by 2 x CO(2) in all three species; though there were few significant growth responses following exposure to 2 x O(3) or the combination of 2 x CO(2) plus 2 x O(3). Results indicate that responses to interacting stressors such as O(3) and CO(2) are species specific.     

Performance of the supported copper oxide catalysts for the catalytic incineration of aromatic hydrocarbons

A fixed bed reactor was used to assess the catalytic incineration of toluene by various transition-metal oxide species supported on gamma-Al(2)O(3). CuO/gamma-Al(2)O(3) was found to be the most active of seven catalysts investigated. The CuO species, with a Cu content of 5% (wt), was hence used with four different supports (CeO(2), gamma-Al(2)O(3), TiO(2) and V(2)O(5)) in order to define the optimal combination. Results of the catalytic incineration of toluene, X-ray diffraction (XRD) analysis, oxygen-temperature programmed desorption (O(2)-TPD), toluene-temperature programmed desorption (toluene-TPD) and hydrogen-temperature programmed reduction (H(2)-TPR) showed that CuO/CeO(2) was the most active catalyst, followed by CuO/gamma-Al(2)O(3). The activity of CuO/CeO(2) with respect to the VOC molecule was observed to follow this sequence: toluen>p-xylene>benzene. The addition of water vapor or CO(2) significantly inhibited the activity of the CuO/CeO(2) and CuO/gamma-Al(2)O(3) catalysts. The inhibiting effect of both was reversible for CuO/gamma-Al(2)O(3). For CuO/CeO(2), the inhibiting effect of CO(2) was reversible and even insignificant at a higher temperature (220 degrees C), but the effect of H(2)O vapor was somewhat irreversible at lower incineration temperatures (220 degrees C). For complete oxidation of toluene, the required reaction temperature increased with gas hourly space velocity (GHSV) and toluene inlet concentration.     

Mechanistic and kinetic study on the ozonolysis of n-butyl vinyl ether, i-butyl vinyl ether and t-butyl vinyl ether

Density functional theory (DFT) and ab initio method are employed to elucidate the mechanisms for O(3)-initiated oxidation of n-butyl vinyl ether (n-BVE) and its isomers (i-BVE and t-BVE). For each BVE, the reactions proceed via O(3) cycloaddition resulting in the formation of primary ozonides (POZs) and then two self-decomposition pathways of POZs are followed. Major products are identified to be formaldehyde and butyl formates (CH(3)CH(2)CH(2)CH(2)OCHO for n-BVE, (CH(3))(2)CHCH(2)OCHO for i-BVE and (CH(3))(3)COCHO for t-BVE). The total and individual rate constants for main product channels have been calculated using the modified multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) approach. At 298 K and 101 kPa, the calculated total rate constants are 2.50×10(-16), 3.41×10(-16) and 4.17×10(-16) cm(3) molecule(-1) s(-1) for n-BVE+O(3), i-BVE+O(3) and t-BVE+O(3), respectively, which are in perfect agreement with experimental results. The total rate coefficients are almost pressure independent in the range of 0.001-101 kPa but obviously positive temperature dependent over the whole study temperature range (200-400 K). Also, the favorable reaction pathways have been determined through the estimation of branching ratios. Moreover, the influence of alkoxy group structure on the reactivity of vinyl ethers was examined.