The Impact of Precipitation Scavenging on the Transport of Trace Gases: A 3-Dimensional Model Sensitivity Study

With the global Chemistry-Transport model MATCHsensitivity simulations were performed to determinethe degree to which especially upward transport ofgases from the earth's surface is limited byconvective and large-scale precipitation scavenging.When only dissolution of species in the liquid phaseis taken into account, mixing ratio reductions in themiddle and upper troposphere by 10% arecalculated for gases with a Henry's Law constant H of10³ mol/l/atm. The removal increases to 50% forH = 10⁴ mol/l/atm, and to 90% for H =10⁵ mol/l/atm. We also consider scavenging by theice phase, which is generally much less efficient thanby the aqueous phase. In fact, rejection of gases fromfreezing water droplets may be a source of trace gasat higher altitudes.H₂O₂ and the strong acids (H₂SO₄,HNO₃, HCl, HBr, HI) have such large solubilitiesthat they become largely removed by precipitation.When significant concentrations of these gases andsulfate aerosol exist above the liquid water domain ofthe atmosphere, they have likely been produced thereor at higher altitudes, although some could have comefrom trace gas rejection from ice particles or fromevaporating hydrometeors. Several other gases areaffected by precipitation, but not strongly enough toprevent fractional transfer to the middle and uppertroposphere: e.g., HNO₄, HNO₂ at pH 5,CH₂O, the organic acids at pH 6,CH₃SOCH₃, HOCl, HOBr, and HOI. NH₃ islargely removed by liquid phase scavenging at pH 7 and SO₂ atpH 7. At pH less thanabout 6, upward transport of SO₂ should largelydepend on the efficiency of oxidation processes in thewater droplets by O₃ and H₂O₂.Most gases have solubilities which are too low forsignificant precipitation scavenging and aqueous phaseoxidation to occur. This holds, e.g., for O₃, CO,the hydrocarbons, NO, NO₂, HCN, CH₃CN,CH₃SCH₃, CH₃O₂H, CH₃CHOandhigher aldehydes, CH₃OH and higher alcohols,peroxyacetylnitrate (PAN), CH₃COCH₃ andother ketones (note that some of these are not listedin Table I because their solubilities are below 10mol/l/atm). Especially for the short-lived gases,transfer from the boundary layer to the middle andupper troposphere is actually promoted by the enhancedupward transport that occurs in clouds.     

Estimates of global N2O emissions from cattle, pig and chicken manure, including a discussion of CH4 emissions

Humans seem to have doubled the global rate of terrestrial nitrogen fixation. Globally 50–70% (85 Tg, 1 Tg=10¹² g) of the nitrogen supplied in fertilizer (80 Tg N/a) and leguminous crops (40–80 Tg N/a) are used to feed cattle. The aim of the present study was to derive some estimates of global N₂O production from animal manure. As the parameter giving the most stable numerical basis for regional and global extrapolation we adopted the molar emission ratios of N₂O to NH₃. These ratios were measured in cattle, pig and chicken housings with different manure handling systems, in dung-heaps and in liquid manure storage tanks. Individual molar emission ratios from outside manure piles varied over two orders of magnitude, strongly dependent on the treatment of the manure. A median emission ratio of 1.6×10^-2 (n=65) was obtained in cow-sheds with slatted floors and liquid manure stored underneath and a median ratio of 24×10^-2 (n=31) was measured in a beef cattle housing with a solid manure handling system.We next extrapolated to global NH₃ emissions from those estimated for Europe, using N uptake by the animals as a scaling factor. Multiplication with observed N₂O to NH₃ ratios next provided some estimates of regional and global N₂O emissions. To account for the great variability of the emission ratios of N₂O/NH₃, we developed upper and lower case emission scenarios, based on lower and upper quartiles of measured emission ratios. The global emission from cattle and swine manure is in the range of 0.2–2.5 Tg N-N₂O/a, representing 44+-39% of the annual atmospheric accumulation rate. This N₂O emission arises from about 40 Tg N/a of cattle and pig manure stored in or at animal housings. We did not account for N₂O emissions from another 50 Tg N/a excreted by grazing cattle, goats and sheep, and application of the manure to agricultural fields. Our study makes it clear that major anthropogenic N₂O emissions may well arise from animal manure. The large uncertainty of emission ratios, which we encountered, show that much more intense research efforts are necessary to determine the factors that influence N₂O emissions from domestic animal manure both in order to derive a more reliable global estimate of N₂O release and to propose alternative waste treatment methods causing smaller N₂O releases. In our studies we found large enhancements in N₂O releases when straw was added to the manure, which is a rather common practice. In view of the ongoing discussion in Europe to re-install the traditional solid manure system (bed down cattle) for environmental and animal welfare reasons, it is noteworthy that our measurements indicate highest N₂O release from this particulary system.In a similar manner, but based on a smaller data set, we also estimated the release of CH₄ from cattle and swine manure and from liquid manure only to be about 9 Tg/year in good agreement with the estimate by the Environmental Protection Agency (1994) of 8.6+-2.6 Tg/year. A total annual methane release as high as 34 Tg/a was derived for solid and liquid cattle and pig manure from animals in housings.     

Methane emission measurements in urban areas in Eastern Germany

We have investigated methane emissions from urban sources in the former East Germany using innovative measurement techniques including a mobile real-time methane instrument and tracer release experiments. Anthropogenic and biogenic sources were studied with the emphasis on methane emissions from gas system sources, including urban distribution facilities and a production plant. Methane fluxes from pressure regulating stations ranged from 0.006 to 24. l/min. Emissions from diffuse sources in urban areas were also measured with concentration maps and whole city flux experiments. The area fluxes of the two towns studied were 0.37 and 1.9 g/m²/s. The emissions from individual gas system stations and total town emissions of this study are comparable to results of similar sites examined in the United States.     

Trace Gas Measurements Between Moscow and Vladivostok Using the Trans-Siberian Railroad

Using a laboratory wagon traveling along the Trans-Siberian railroad, O₃, NO, NO₂, CO, CH₄, SF₆ and black carbon aerosol have been measured during the summer of 1996. The expedition from Niznij Novgorod (500 km east of Moscow) to Vladivostok (and back to Moscow) has shown the great potential of the train method; here the first results are presented and discussed. A wealth of boundary layer air data was obtained during the over 18000 km travel without serious contamination problems from the electric train itself. The diurnal O₃ cycle peaked generally below 50 nmole/mole, showed the effects of changes in J(NO₂), and often dropped to a few nmole/mole at night time during inversions. Over the vast Siberian lowlands situated between the Ural mountains and the river Yenisey, CH₄ levels were consistently elevated at around 1.95 µmole/mole, which we mainly attribute to wetland emissions. Over eastern Siberia, however, CH₄ levels were generally lower at 1.85 µmole/mole. In contrast, over the west Siberian lowlands, CO levels were relatively low, often reaching values of only 110 nmole/mole, whereas over eastern Siberia CO levels were higher. Very high CO levels were detected over a 2000 km section east of Chita, along the river Amur, which represented an enormous polluted air mass. ¹⁴C analysis performed on several CO samples confirms that the origin was biomass burning. SF₆, which was measured as a general conserved tracer, showed an eastward attenuation from 4.0 to 3.9 pmole/mole, with peaks in a number of places due to local Russian emissions.     

Synthetic shorelines in New Zealand? Quantification and characterisation of microplastic pollution on Canterbury's coastlines

Microplastics are persistent environmental contaminants found in marine environments worldwide. Microplastic particles isolated from coastlines in the Canterbury region of New Zealand were quantified and characterised. Sediment samples were collected from 10 locations representing exposed-beach, estuarine and harbour environments in both urban and non-urban settings. Particles were isolated from sediments using an NaCl density-separation procedure and quantified and characterised with a combination of optical/fluorescence imaging and micro-Raman spectroscopy. Microplastics were detected at eight out of 10 locations, at concentrations ranging from 0–45.4 particles kg^?1 of dry sediment. The majority of microplastics were identified as polystyrene (55%), polyethylene (21%) and polypropylene (11%). Microplastic concentrations in exposed-beach environments were significantly greater than in harbour and estuarine environments.     

塔里木盆地库鲁克塔格地区二叠纪末-中三叠世基性岩床的发现及其地质意义

新疆塔里木盆地东北缘库鲁克塔格地区的中寒武统莫合尔山组沉积地层中发现三条形成于二叠纪末到中三叠世的基性岩床。三条岩床沿沉积岩层面顺层侵入,按照从下到上的顺序,分别为辉绿岩床(厚3m)、辉长岩床(厚20m)和粗玄岩床(厚2.5m)。三条岩床的地球化学特征相似,稀土含量高(∑REE=210×10^-6~297×10^-6),轻稀土元素富集((La/Yb)_N =13.54~17.96),Eu负异常不明显(δEu=0.97~1.21),Ce稍具正异常(δCe=1.11~1.25)。大离子亲石元素(Rb、Ba、Th、Sr)富集,Sr具明显正异常; Ta、Nb和Hf具负异常。低氧化度(0.13~0.40)。三条岩床为同源岩浆活动的产物,岩浆源于上地幔或下地壳,但有下陆壳成分混染。三个样品的MgO含量在4%~6%之间,Mg^#值在37.6~55.6之间,固结指数SI值位于18.7~29.3之间,反映原始的岩浆经历了比较明显的分异作用。粗玄岩床K-Ar年龄为255.2±7.3Ma,辉绿岩床K-Ar年龄为242.8±5.7Ma,辉长岩床Ar-Ar年龄为229.7±3.7Ma。本次岩浆侵入事件发生在南天山洋闭合之后,构造背景为造山后碰撞伸展环境。     

Learning about ozone depletion

Stratospheric ozone depletion has been much studied as a case history in the interaction between environmental science and environmental policy. The positive influence of science on policy is often underscored, but here we review the photochemistry of ozone in order to illustrate how scientific learning has the potential to mislead policy makers. The latter may occur particularly in circumstances where limited observations are combined with simplified models of a complex system, such as may generally occur in the global change arena. Even for the well-studied case of ozone depletion, further research is needed on the dynamics of scientific learning, particularly the scientific assessment process, and how assessments influence the development of public policy.     

The effect of low-level kelp supplementation on digestive enzyme activity levels in cultured abalone Haliotis midae fed formulated feeds

Previous studies have found that macroalgal inclusion in formulated diets for cultured abalone improves feed utilisation, and it was suggested that seaweed-associated bacteria supply enzymes that aid in the animal's digestion. In the present study, we hypothesised that kelp supplementation in formulated feed affects the profile of digestive enzymes in farmed Haliotis midae. Commercially reared sub-adult abalone fed a kelp-supplemented (Ecklonia maxima; 0.88% dry weight) or kelp-free control feed were collected for analysis of the amylase, alginate lyase, laminarinase, fucoidanase and protease activities in the gut. Levels of polysaccharidase and protease activity did not significantly differ between the diet treatments. However, enzyme-activity levels were more variable in abalone fed the kelp-free diet as compared with those fed the kelp-supplemented diet (coefficients of variation: 73%, 48.3–60.2% and 31.9% [control diet] versus 42.7%, 13.6–33.8% and 14.6% [KS diet] for amylase, macroalgal polysaccharidases and acid protease activity, respectively). We suggest that the presence of dietary kelp modulates the abalone's gut bacteria and their nutrient exchange. Proteomic identification of proteins in abalone gut sections showed that exogenous enzymes associated with the gut microbiome aid in bacterial utilisation of digested molecules, whereas abalone endogenous enzymes degrade the macronutrients in formulated feeds.     

Chemical budgets of the stratosphere

A review is given of the stratospheric budgets of odd oxygen, odd nitrogen, nitrous oxide, methane and carbonyl sulfide. The stratospheric column production rate of NO by the reaction N₂O + O(¹D) → 2 NO is 1.1–1.9 × 10⁸ molecules cm^?2 s^?1. The stratospheric loss rates for N₂O, CH₄ and COS are equal to 0.9–1.4 × 10⁹, 1 × 10¹⁰ and 0.5 × 10⁷ molecules cm^?2 s^?1, respectively. From currently available information on the global distributions of N₂O and CH₄ there are some indications of about two times smaller OH concentrations below 35 km than those which are calculated based on the latest compilation of kinetic data.Most significantly, however, it is shown that photochemical models and available ozone observations cannot be reconciled and that there may be particularly severe problems in the 25–35 km region. This issue is thoroughly discussed.Volcanic emissions of SO₂ to the stratosphere may locally lead to much enhanced ozone concentrations and heating rates. These may influence the dynamic behaviour of volcanic plumes before their dispersion over large volumes of the stratosphere.