Displacement of Zn through acidic light-textured soils

In order to gain understanding of the movement of pollutant metals in soil. the chemical mechanisms involved in the transport of zinc were studied. The displacement of zinc through mixtures of sand and cation exchange resin was measured to validate the methods used for soil. With cation exchange capacities of 2.5 and 5.0 cmol(c) kg(-1). 5.6 and 8.4 pore volumes of 10 mM CaCl2, respectively, were required to displace a pulse of ZnCl2. A simple Burns-type model (Wineglass) using an adsorption coefficient (K-d) determined by fitting a straight line relationship to an adsorption isotherm gave a good fit to the data (K-d=0.73 and 1.29 ml g(-1), respectively). Surface and subsurface samples of an acidic sandy loam (organic matter 4.7 and 1.0%. cation exchange capacity (CEC) 11.8 and 6.1 cmol(c) kg(-1) respectively) were leached with 10 mM calcium chloride. nitrate and perchlorate. With chloride. the zinc pulse was displaced after 25 and 5 pore volumes, respectively. The Kd values were 6.1 and 2.0 ml g(-1). but are based on linear relationships fitted to isotherms which are both curved and show hysteresis. Thus. a simple model has limited value although it does give a general indication of rate of displacement. Leaching with chloride and perchlorate gave similar displacement and Kd values, but slower movement occurred with nitrate in both soil samples (35 and 7 pore volumes, respectively) which reflected higher Kd values when the isotherms were measured using this anion (7.7 and 2.8 ml g(-1) respectively). Although pH values were a little hi-her with nitrate in the leachates, the differences were insufficient to suggest that this increased the CEC enough to cause the delay. No increases in pH occurred with nitrate in the isotherm experiments. Geochem was used to calculate the proportions of Zn complexed with the three anions and with fulvic acid determined from measurements of dissolved organic matter. In all cases, more than 91% of the Zn was present as Zn2+ and there were only minor differences between the anions. Thus, there is an unexplained factor associated with the greater adsorption of Zn in the presence of nitrate. Because as little as five pore volumes of solution displaced Zn through the subsurface soil, contamination of ground waters may be a hazard where Zn is entering a light-textured soil, particularly where soil salinity is increased. Reductions in organic matter content due to cultivation will increase the hazard. (C) 2004 Elsevier B.V. All rights reserved.

Bt-cotton boosts the gross margin of small-scale cotton producers in South Africa

This paper explores some of the issues involved in the Genetic Modification (GM) debate by focusing on one crop that has been modified for pest resistance, cotton (Gossypium hirsutum), and commercially released to small-scale farmers in the Makhathini Flats, KwaZulu Natal, the Republic of South Africa. This was the first commercial release of a GM variety (Bt-cotton) in Sub-Saharan Africa, and thus provides valuable and timely insights into some of the potential advantages and disadvantages of the technology for small-scale farmers in Africa. Even though there are wider concerns regarding the vulnerability of small-scale farmers in the area, the survey results suggest that Bt-cotton generated higher yields and gross margins than non-Bt-cotton. In addition, Bt-cotton significantly reduced the use of pesticide with consequent potential benefits to human health and the environment.

A weaker Agulhas Current leads to more Agulhas leakage

Time series of transports in the Agulhas region have been constructed by simulating Lagrangian drifter trajectories in a 1/10 degree two-way nested ocean model. Using these 34 year long time series it is shown that smaller (larger) Agulhas Current transport leads to larger (smaller) Indian-Atlantic inter-ocean exchange. When transport is low, the Agulhas Current detaches farther downstream from the African continental slope. Moreover, the lower inertia suppresses generation of anti-cyclonic vorticity. These two effects cause the Agulhas retroflection to move westward and enhance Agulhas leakage. In the model a 1 Sv decrease in Agulhas Current transport at 32°S results in a 0.7 ± 0.2 Sv increase in Agulhas leakage.

Simple and surprisingly effective one-step extraction-cleanup by Soxflo for DDT and its metabolites from environmental samples

A pilot study found that DDT breakdown at the GC inlet was extensive in extracts from some-but not all-samples with high organic carbon contents. However, DDT losses could be prevented with a one-step extraction-cleanup in the Soxflo instrument with dichloromethane and charcoal. This dry-column procedure took 1 h at room temperature. It was tested on spiked soil and peat samples and validated with certified soil and sediment reference materials. Spike recoveries from freshly spiked samples ranged from 79 to 111% at 20-4000 mug/kg concentrations. Recoveries from the real-world CRMs were 99.7-100.2% of DDT, 89.7-90.4% of DDD and 89.6-107.9% of DDE. It was concluded that charcoal cleanups should be used routinely during surveys for environmental DDX pollution in order to mitigate against unpredictable matrix-enhanced breakdown in the GC. (C) 2004 Elsevier B.V. All rights reserved.

Comparative study of oestrogenic properties of eight phytoestrogens in MCF7 human breast cancer cells

Previous studies have compared the oestrogenic properties of phytoestrogens in a wide variety of disparate assays. Since not all phytoestrogens have been tested in each assay, this makes inter-study comparisons and ranking oestrogenic potency difficult. In this report, we have compared the oestrogen agonist and antagonist activity of eight phytoestrogens (genistein, daidzein, equol, miroestrol, deoxymiroestrol, 8-prenylnaringenin, coumestrol and resveratrol) in a range of assays all based within the same receptor and cellular context of the MCF7 human breast cancer cell line. The relative binding of each phytoestrogen to oestrogen receptor (ER) of MCF7 cytosol was calculated from the molar excess needed for 50 % inhibition of [H-3]oestradiol binding (IC50), and was in the order coumestrol (35x)/8-prenylnaringenin (45 x)/deoxymiroestrol (50 x) > miroestrol (260x) > genistein (1000x) > equol (4000x) > daidzein (not achieved: 40 % inhibition at 10(4)-fold molar excess) > resveratrol (not achieved: 10 % inhibition at 10(5)-fold molar excess). For cell-based assays, the rank order of potency (estimated in terms of the concentration needed to achieve a response equivalent to 50 % of that found with 17 beta-oestradiol (IC50)) remained very similar for all the assays whether measuring ligand ability to induce a stably transfected oestrogen-responsive ERE-CAT reporter gene, cell growth in terms of proliferation rate after 7 days or cell growth in terms of saturation density after 14 days. The IC50 values for these three assays in order were for 17 beta-oestradiol (1 x 10-(11) M, 1 x 10-(11) M, 2 x 10(-11) M), and in rank order of potency for the phytoestrogens, deoxymiroestrol (1 x 10(-10) M, 3 x 10(-11) M, 2 x 10(-11) M) > miroestrol (3 x 10(-10) M, 2 x 10(-11) M, 8 x 10(-11) M) > 8-prenylnaringenin (1 x 10(-9) M, 3 x 10(-10) M, 3 x 10(-10) M) > cournestrol (3 x 10(-8) M, 2 x 10(-8) M, 3 x 10(-8) M) > genistein (4 x 10(-8) M, 2 x 10(-8) M, 1 x 10(-8) M)/equol (1 x 10(-7) M, 3 x 10(-8) M, 2 x 10(-8) M) > daidzein (3 x 10(-7) M, 2 x 10(-7) M, 4 x 10(-8) M) > resveratrol (4 x 10(-6) M, not achieved, not achieved). Despite using the same receptor context of the MCF7 cells, this rank order differed from that determined from receptor binding. The most marked difference was for cournestrol and 8-prenylnaringenin which both displayed a relatively potent ability to displace [3H]oestradiol from cytosolic ER compared with their much lower activity in the cell-based assays. Albeit at varying concentrations, seven of the eight phytoestrogens (all except resveratrol) gave similar maximal responses to that given by 17 beta-oestradiol in cell-based assays which makes them full oestrogen agonists. We found no evidence for any oestrogen antagonist action of any of these phytoestrogens at concentrations of up to 10(-6) M on either reporter gene induction or on stimulation of cell growth. (c) 2005 Elsevier Ltd. All rights reserved.

Methylene spacer-regulated structural variation in cobalt(II/III) complexes with bridging acetate and Salen- or Salpn-type Schiff-base ligands

Two linear, trinuclear mixed-valence complexes, [Co-II{(mu-L-1)(mu-OAc)Co-III (OAc)}(2)] (1) and [Co-II(mu-L-2) (mu-OAc)Co-III(OAc)}(2)] (2) and two mononuclear Con' complexes [Co-III{L-3)(OAc)] (3), and [Co-III {L-4}(OAc)] (4) were prepared and the molecular structures of 1, 2 and 4 elucidated on the basis of X-ray crystallography [OAc = Acetate ion, H2L1 = H(2)Salen 1,6-bis(2-hydroxyphenyl)-2,5-diazahexa-1,5-diene, H2L2 H2Me2-Salen = 2,7-bis(2-hydroxyphenyl)-2,6-diazaocta-2,6-diene, H2L3 = H(2)Salpn = 1,7-bis(2-hydroxyphenyl)-2,6-diazahepta1,6-diene, H2L4 = H(2)Me(2)Salpn = 2,8-bis(2-hydroxyphenyl)3,7-diazanona-2,7-dienel. In complexes I and 2, the acetate groups show both monodentate and bridging bidentate coordination modes, whereas chelating bidentate acetate is present in 4. The terminal (CoN2O4)-N-III centres in 1 and 2 exhibit uniform facial arrangements of both non-bridged N2O and bridging O-3 donor sets and the Co-II centre is coordinated to six (four phenoxo and two acetato) oxygen atoms of the bridging ligands. The effective magnetic moment at room temperature corresponds to the presence of high-spin Coll in both 1 and 2. The complexes 1 and 2 are thus Co-III(S = 0)Co-II(S = 3/2)-Co-II(S = 0) trimers. Complexes 3 and 4 are monomeric and diamagnetic containing low-spin Co-III(S = 0) with chelating tetradentate Schiff base and bidentate acetate. Calculations based on DFT rationalise the formation of trinuclear or monomiclear complexes. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Influence of a halide ion on ribbons of water pentamer

Reactions of CuF2, CuCl2 center dot 2H(2)O and CuBr2 with 2,2'-dipyridylamine (HDPA) in water at room temperature using Cu: HDPA = 2: 1 mol yield [Cu(HDPA) (H2O)(2)F]F center dot 3H(2)O (1), Cu(HDPA) Cl-2 (2) and [Cu(HDPA) Br-2 (3) respectively. The structures of 2 and 3 are isostructural in spacegroup C-2 with cell dimensions; for 2, a = 14.702(8), b = 7.726(2), c = 4.829(6) angstrom, beta = 96.68(8)degrees and for 3, a = 14.2934(8), b = 7.9057(6), c = 5.1982(5) angstrom, beta = 94.049(7)degrees. In the X-ray crystal structure, the complex 1 is found to contain tapes of water pentamers. Our DFT calculations at the B3LYP/LanL2DZ level show that the reaction Cu(HDPA)X-2 + 2H(2)O = [Cu(HDPA)(H2O)(2)X]X is most exothermic in the gas phase when X- = F-, i.e., the tendency of water uptake is maximum for Cu(HDPA) F-2. It seems that the exothermicities of the aquations of Cu(HDPA) Cl-2 and Cu(HDPA) Br-2 are not sufficient to stabilise the type of ribbons of water observed in 1 and consequently water is eschewed when X- = Cl- or Br-.

Syntheses, structural analyses, and magneto-structural correlations of three polymeric Fe(II) complexes with azide ligand

Three new metal-organic polymeric complexes, [Fe(N-3)(2)(bPP)(2)] (1), [Fe(N-3)(2)(bpe)] (2), and [Fe(N-3)(2)(phen)] (3) [bpp = (1,3-bis(4-pyridyl)-propane), bpe = (1,2-bis(4-pyridyl)-ethane), phen = 1,10-phenanthroline], have been synthesized and characterized by single-crystal X-ray diffraction studies and low-temperature magnetic measurements in the range 300-2 K. Complexes 1 and 2 crystallize in the monoclinic system, space group C2/c, with the following cell parameters: a = 19.355(4) Angstrom, b = 7.076(2) Angstrom, c = 22.549(4) Angstrom, beta = 119.50(3)degrees, Z = 4, and a = 10.007(14) Angstrom, b = 13.789(18) Angstrom, c = 10.377(14) Angstrom, beta = 103.50(1)degrees, Z = 4, respectively. Complex 3 crystallizes in the triclinic system, space group P (1) over bar, with a = 7.155(12) Angstrom, b = 10.066(14) Angstrom, c = 10.508(14) Angstrom, alpha = 109.57(1)degrees, beta = 104.57(1)degrees, gamma = 105.10(1)degrees, and Z = 2. All coordination polymers exhibit octahedral Fe(II) nodes. The structural determination of 1 reveals a parallel interpenetrated structure of 2D layers of (4,4) topology, formed by Fe(II) nodes linked through bpp ligands, while mono-coordinated azide anions are pendant from the corrugated sheet. Complex 2 has a 2D arrangement constructed through 1D double end-to-end azide bridged iron(11) chains interconnected through bpe ligands. Complex 3 shows a polymeric arrangement where the metal ions are interlinked through pairs of end-on and end-to-end azide ligands exhibiting a zigzag arrangement of metals (Fe-Fe-Fe angle of 111.18degrees) and an intermetallic separation of 3.347 Angstrom (through the EO azide) and of 5.229 Angstrom (EE azide). Variable-temperature magnetic susceptibility data suggest that there is no magnetic interaction between the metal centers in 1, whereas in 2 there is an antiferromagnetic interaction through the end-to-end azide bridge. Complex 3 shows ferro- as well as anti-ferromagnetic interactions between the metal centers generated through the alternating end-on and end-to-end azide bridges. Complex I has been modeled using the D parameter (considering distorted octahedral Fe(II) geometry and with any possible J value equal to zero) and complex 2 has been modeled as a one-dimensional system with classical and/or quantum spin where we have used two possible full diagonalization processes: without and with the D parameter, considering the important distortions of the Fe(II) ions. For complex 3, the alternating coupling model impedes a mathematical solution for the modeling as classical spins. With quantum spin, the modeling has been made as in 2.

Supramolecular hydrogen-bond structures and magnetic interactions in basal-apical, dinuclear, azide-bridged copper(II) complexes

The synthesis, characterisation, X-ray single crystal structures and magnetic properties of three new basal-apical mu(2)-1,1-azide-bridged complexes [(CuLN3)-N-1](2) (1), [(CuLN3)-N-2](2) (2) and [(CuLN3)-N-3](2) (3) with very similar tridentate Schiff-base blocking ligands {HL1 = N-[2-(ethylamino) ethyl] salicylaldimine; HL2 = 7-(ethylamino)-4-methyl-5-azahept-3-en-2-one; HL3 = 7-amino-4-methyl-5-azaoct-3-en-2-one} have been reported [complex 1: monoclinic, P2(1)/c, a = 8.390(2), b = 7.512(2), c = 19.822(6) Angstrom, beta = 91.45(5)degrees; complex 2: monoclinic, P2(1)/c, a = 8.070(9), b = 9.787(12), c = 15.743(17) A, beta = 98.467(10)degrees; complex 3: monoclinic, P2(1)/n, a = 5.884(7), b = 16.147(18), c = 11.901(12) Angstrom, beta = 90.050(10)degrees]. The structures consist of neutral dinuclear entities resulting from the pairing of two mononuclear units through end-on azide bridges connecting an equatorial position of one copper centre to an axial position of the other, The copper ions adopt a (4+1) square-based geometry in all the complexes. In complex 2, there is no inter-dimer hydrogen-bonding. However, complexes 1 and 3 form two different supramolecular structures in which the dinuclear entities are linked by H-bonds giving one-dimensional systems. Variable temperature (300-2 K) magnetic-susceptibility measurements and magnetisation measurements at 2 K reveal that all three complexes have antiferromagnetic coupling. Magneto-structural correlations have been made taking into consideration both the azido bridging ligands and the existence of intermolecular hydrogen bonds. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

The thermal transformations of bicyclopropylidene and methylenespiropentane revisited

The overall and the individual rate constants of the unimolecular thermal isomerization of methylenespiropentane (4) to 1,2- and 1,3-dimethylenecyclobutanes (7 and 8) have been determined to be lg (k(-4)/s(-1)) = (13.78 +/- 0.06) - (49.7 +/- 0.2) kcal mol(-1)/RT.ln 10, lg(k(7)/s(-1)) = (13.03 +/- 0.19) - (48.0 +/- 0.6) kcal mol(-1)/RT.ln 10 and lg(k(8)/s(-1)) = (14.15 +/- 0.19) - (52.4 +/- 0.5) kcal mol(-1)/RT.ln 10, respectively. The activation energies are significantly lower than that for the rearrangement of the parent spiropentane. ((c) Wiley-VCH Verlag GmbH & Co.

Effect of forage type and proportion of concentrate in the diet on milk fatty acid composition in cows given sunflower oil and fish oil

Based on the potential benefits of cis-9, trans- 11 conjugated linoleic acid (CLA) for human health there is a need to develop effective strategies for enhancing milk fat CLA concentrations. In this experiment, the effect of forage type and level of concentrate in the diet on milk fatty acid composition was examined in cows given a mixture of fish oil and sunflower oil. Four late lactation Holstein-British Friesian cows were used in a 4 x 4 Latin-square experiment with a 2 x 2 factorial arrangement of treatments and 21-day experimental periods. Treatments consisted of grass (G) or maize (M) silage supplemented with low (L) or high (H) levels of concentrates (65: 35 and 35: 65; forage: concentrate ratio, on a dry matter (DM) basis, respectively) offered as a total mixed ration at a restricted level of intake (20 kg DM per day). Lipid supplements (30 g/kg DM) containing fish oil and sunflower oil (2: 3 w/w) were offered during the last 14 days of each experimental period. Treatments had no effect on total DM intake, milk yield, milk constituent output or milk fat content, but milk protein concentrations were lower (P<0.05) for G than M diets (mean 43.0 and 47.3 g/kg, respectively). Compared with grass silage, milk fat contained higher (P<0.05) amounts Of C-12: 0, C-14: 0, trans C-18:1 and long chain >= C20 (n-3) polyunsaturated fatty acids (PUFA) and lower (P<0.05) levels Of C-18:0 and trans C-18:2 when maize silage was offered. Increases in the proportion of concentrate in the diet elevated (P<0.05) C-18:2 (n-6) and long chain >= C20 (n-3) PUFA content, but reduced (P<0.05) the amount Of C-18:3 (n-3). Concentrations of trans-11 C-18:1 in milk were independent of forage type, but tended (P<0.10) to be lower for high concentrate diets (mean 7.2 and 4.0 g/100 g fatty acids, for L and H respectively). Concentrations of trans-10 C-18:1 were higher (P<0.05) in milk from maize compared with grass silage (mean 10.3 and 4.1 g/100 g fatty acids, respectively) and increased in response to high levels of concentrates in the diet (mean 4.1 and 10.3 g/100 g fatty acids, for L and H, respectively). Forage type had no effect (P>0.05) on total milk conjugated linoleic acid (CLA) (2.7 and 2.8 g/100 g fatty acids, for M and G, respectively) or cis-9, trans-11 CLA content (2.2 and 2.4 g/100 g fatty acids). Feeding high concentrate diets tended (P<0.10) to decrease total CLA (3.3 and 2.2 g/100 g fatty acids, for L and H, respectively) and cis-9, trans-11 CLA (2.9 and 1/7 g/100 g fatty acids) concentrations and increase milk trans-9, cis-11 CLA and trans-10, cis-12 CLA content. In conclusion, the basal diet is an important determinant of milk fatty acid composition when a supplement of fish oil and sunflower oil is given.

Cyclam derivatives containing three acetate pendant arms: synthesis, acid-base, metal complexation and structural studies

The ligands 1,4,8,11-tetraazacyclotetradecane-1,4,8-triacetic-11-methylphosphonic acid (H(5)te3a1p) and 1,4,8,11-tetraazacyclotetradecane-1,4,8-triacetic acid (H(3)te3a) were synthesized, the former one for the first time. The syntheses of these ligands were achieved from reactions on 1,4,8,11-tetraazacyclotetradecane-1,4,8-tris( carbamoylmethyl) hydroiodide (te3am center dot HI), and compounds (Hte3am)(+), 1, and (H(7)te3a1p)(2+), 4, were characterized by X-ray diffraction. Structures of two other compounds resulting from side-reactions, (H(2)te2lac)(2+), 2, and (H(4)te2a2p(OEt2))(2+), 3, were also determined by X-ray diffraction. Potentiometric titrations of H(5)te3a1p and H(3)te3a were performed at 298.2 K and ionic strength 0.10 mol dm(-3) in NMe4NO3 to determine their protonation constants. H-1 and P-31 NMR titrations of H(5)te3a1p were carried out in order to determine the very high first protonation constant of this ligand and to elucidate the sequence of protonation. Potentiometric studies of the two ligands with Ca2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ metal ions performed in the same experimental conditions showed that the complexes of H5te3a1p present very high thermodynamic stability while complexes of H(3)te3a, particularly Co2+ and Zn2+, are even more stable. P-31 NMR spectra of the cadmium(II) complex of H(5)te3a1p showed that the phosphonate moiety was coordinated to the metal ion. The UV-vis-NIR spectroscopic data and magnetic moment values of Co2+ and Ni2+ complexes of H(5)te3a1p and H(3)te3a together with the EPR of the corresponding Cu2+ complexes indicated that all these complexes adopt distorted octahedral coordination geometries in solution. This was confirmed by the single crystal structure of [Cu-2(Hte3a)(H2O)(3)Cl]Cl-0.5(ClO4)(0.5) center dot 2H(2)O that showed two distorted octahedral copper centres bridged by a N-acetate pendant arm with a Cu center dot center dot center dot Cu distance of 4.890(1) angstrom. The first one is encapsulated into the macrocyclic cavity surrounded by four nitrogen and two oxygen donors from the macrocycle, whereas the second one is on the periphery of the macrocycle and is coordinated to two oxygen atoms of one acetate pendant arm in chelating fashion, one chloride and three water molecules.

Soya isoflavone-enriched cereal bars affect markers of endothelial function in postmenopausal women

Soya isoflavones are thought to be cardioprotective due to their structural similarity to oestrogen. In order to investigate the effect of soya isoflavones on markers of endothelial function we conducted a randomised, double-blind, placebo-controlled, cross-over study with thirty healthy postmenopausal women. The women consumed cereal bars, with or without soya isoflavones (50 mg/d), for 8 weeks, separated by an 8-week washout period. Systemic arterial complince (SAC), isobaric arterial compliance (IAC), flow-mediated endothelium-dependent vasodilation (FMD) and nitroglycerine-mediated endothelium-independent vasodilation (NMD) were measured at the beginning of the study and after each intervention period. Blood pressure (BP) and plasma concentrations of nitrite and nitrate (NOx) and endothelin-1 (ET-1) were measured at the beginning and end of each intervention period. NMD was 13.4 (sem 2.0) % at baseline and 15.5 (sem 1.1) % after isoflavone treatment compared with 12.4 (sem 1.0) % after placebo treatment (P=0.03). NOx increased from 27.7 (sem 2.7) to 31.1 (sem 3.2) mu m after isoflavones treatment compared with 25.4 (sem 1.5) to 20.4 (sem 1.1) mu m after placebo treatment (P=0.003) and a significant increase in the NOx:ET-1 ratio (P=0.005) was observed after the isoflavone treatment compared with placebo. A significant difference in SAC after the isoflavone and placebo treatment was observed (P=0.04). No significant difference was found in FMD, IAC, BP and ET-1. In conclusion, 8 weeks' consumption of cereals bars enriched with 50 mg soya isoflavones/d increased plasma NOx concentrations and improved endothelium-independent vasodilation in healthy postmenopausal women.

The impact of traffic emissions on atmospheric ozone and OH: results from QUANTIFY

To estimate the impact of emissions by road, aircraft and ship traffic on ozone and OH in the present-day atmosphere six different atmospheric chemistry models have been used. Based on newly developed global emission inventories for road, ship and aircraft emission data sets each model performed sensitivity simulations reducing the emissions of each transport sector by 5%. The model results indicate that on global annual average lower tropospheric ozone responds most sensitive to ship emissions (50.6%±10.9% of the total traffic induced perturbation), followed by road (36.7%±9.3%) and aircraft exhausts (12.7%±2.9%), respectively. In the northern upper troposphere between 200–300 hPa at 30–60° N the maximum impact from road and ship are 93% and 73% of the maximum effect of aircraft, respectively. The latter is 0.185 ppbv for ozone (for the 5% case) or 3.69 ppbv when scaling to 100%. On the global average the impact of road even dominates in the UTLS-region. The sensitivity of ozone formation per NOx molecule emitted is highest for aircraft exhausts. The local maximum effect of the summed traffic emissions on the ozone column predicted by the models is 0.2 DU and occurs over the northern subtropical Atlantic extending to central Europe. Below 800 hPa both ozone and OH respond most sensitively to ship emissions in the marine lower troposphere over the Atlantic. Based on the 5% perturbation the effect on ozone can exceed 0.6% close to the marine surface (global zonal mean) which is 80% of the total traffic induced ozone perturbation. In the southern hemisphere ship emissions contribute relatively strongly to the total ozone perturbation by 60%–80% throughout the year. Methane lifetime changes against OH are affected strongest by ship emissions up to 0.21 (± 0.05)%, followed by road (0.08 (±0.01)%) and air traffic (0.05 (± 0.02)%). Based on the full scale ozone and methane perturbations positive radiative forcings were calculated for road emissions (7.3±6.2 mWm−2) and for aviation (2.9±2.3 mWm−2). Ship induced methane lifetime changes dominate over the ozone forcing and therefore lead to a net negative forcing (−25.5±13.2 mWm−2).