Chemical and aerosol characterisation of the troposphere over West Africa during the monsoon period as part of AMMA

During June, July and August 2006 five aircraft took part in a campaign over West Africa to observe the aerosol content and chemical composition of the troposphere and lower stratosphere as part of the African Monsoon Multidisciplinary Analysis (AMMA) project. These are the first such measurements in this region during the monsoon period. In addition to providing an overview of the tropospheric composition, this paper provides a description of the measurement strategy (flights performed, instrumental payloads, wing-tip to wing-tip comparisons) and points to some of the important findings discussed in more detail in other papers in this special issue. The ozone data exhibits an "S" shaped vertical profile which appears to result from significant losses in the lower troposphere due to rapid deposition to forested areas and photochemical destruction in the moist monsoon air, and convective uplift of ozone-poor air to the upper troposphere. This profile is disturbed, particularly in the south of the region, by the intrusions in the lower and middle troposphere of air from the southern hemisphere impacted by biomass burning. Comparisons with longer term data sets suggest the impact of these intrusions on West Africa in 2006 was greater than in other recent wet seasons. There is evidence for net photochemical production of ozone in these biomass burning plumes as well as in urban plumes, in particular that from Lagos, convective outflow in the upper troposphere and in boundary layer air affected by nitrogen oxide emissions from recently wetted soils. This latter effect, along with enhanced deposition to the forested areas, contributes to a latitudinal gradient of ozone in the lower troposphere. Biogenic volatile organic compounds are also important in defining the composition both for the boundary layer and upper tropospheric convective outflow. Mineral dust was found to be the most abundant and ubiquitous aerosol type in the atmosphere over Western Africa. Data collected within AMMA indicate that injection of dust to altitudes favourable for long-range transport (i.e. in the upper Sahelian planetary boundary layer) can occur behind the leading edge of mesoscale convective system (MCS) cold-pools. Research within AMMA also provides the first estimates of secondary organic aerosols across the West African Sahel and have shown that organic mass loadings vary between 0 and 2 μg m−3 with a median concentration of 1.07 μg m−3. The vertical distribution of nucleation mode particle concentrations reveals that significant and fairly strong particle formation events did occur for a considerable fraction of measurement time above 8 km (and only there). Very low concentrations were observed in general in the fresh outflow of active MCSs, likely as the result of efficient wet removal of aerosol particles due to heavy precipitation inside the convective cells of the MCSs. This wet removal initially affects all particle size ranges as clearly shown by all measurements in the vicinity of MCSs.

Observed and simulated precipitation responses in wet and dry regions 1850–2100

Global warming is expected to enhance fluxes of fresh water between the surface and atmosphere, causing wet regions to become wetter and dry regions drier, with serious implications for water resource management. Defining the wet and dry regions as the upper 30% and lower 70% of the precipitation totals across the tropics (30° S–30° N) each month we combine observations and climate model simulations to understand changes in the wet and dry regions over the period 1850–2100. Observed decreases in precipitation over dry tropical land (1950–2010) are also simulated by coupled atmosphere–ocean climate models (−0.3%/decade) with trends projected to continue into the 21st century. Discrepancies between observations and simulations over wet land regions since 1950 exist, relating to decadal fluctuations in El Niño southern oscillation, the timing of which is not represented by the coupled simulations. When atmosphere-only simulations are instead driven by observed sea surface temperature they are able to adequately represent this variability over land. Global distributions of precipitation trends are dominated by spatial changes in atmospheric circulation. However, the tendency for already wet regions to become wetter (precipitation increases with warming by 3% K−1 over wet tropical oceans) and the driest regions drier (precipitation decreases of −2% K−1 over dry tropical land regions) emerges over the 21st century in response to the substantial surface warming.

Aerosol and precipitation chemistry measurements in a remote site in Central Amazonia: the role of biogenic contribution

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chemical composition and metabolizable energy values of corn germ meal obtained by wet milling for layers

An experiment was carried out to determine the chemical composition, metabolizable energy values, and coefficients of nutrient digestibility of corn germ meal for layers. The chemical composition of corn germ meal was determined, and then a metabolism assay was performed to determine its apparent metabolizable energy (AME) and apparent metabolizable energy corrected for nitrogen (AMEn) values and its dry matter and gross energy apparent metabolizability coefficients (CAMDM and CAMGE, respectively). In the 8-day assay (four days of adaptation and four days of total excreta collection), 60 29-week-old white Lohman LSL layers were used. A completely randomized experimental design, with three treatments with five replicates of four birds each, was applied. Treatments consisted of a reference diet and two test diets, containing 20 or 30% corn germ meal. Results were submitted to analysis of variance and means were compared by the Tukey tests at 5% probability level. The chemical composition of corn germ meal was: 96.39% dry matter, 49.48% ether extract, 1.87% ashes, 7243 kcal gross energy/kg, 11.48% protein, 0.19% methionine, 0.21% cystine, 0.48% lysine, 0.40% threonine, 0.72% arginine, 0.35% isoleucine, 0.83% leucine, 0.57% valine, and 0.37% histidine, on as-fed basis. There were no statistical differences in AME, AMEn, CAMDM, and CAMGE values with the inclusion of 20 and 30% corn germ meal in the diets. On dry matter basis, AME, AMEn, CAMDM, and CAMGE values of corn germ meal were: 4,578 and 4,548 kcal/kg, 4,723 and 4,372 kcal/kg, 64.95 and 61.86%, respectively.

Physical-chemical characterization and wet milling yield of four maize hybrids

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aerosol and precipitation chemistry measurements in a remote site in Central Amazonia: the role of biogenic contribution

In this analysis a 3.5 years data set of aerosol and precipitation chemistry, obtained in a remote site in Central Amazonia (Balbina, (1A degrees 55' S, 59A degrees 29' W, 174 m a.s.l.), about 200 km north of Manaus) is discussed. Aerosols were sampled using stacked filter units (SFU), which separate fine (d < 2.5 mu m) and coarse mode (2.5 mu m < d < 10.0 mu m) aerosol particles. Filters were analyzed for particulate mass (PM), Equivalent Black Carbon (BCE) and elemental composition by Particle Induced X-Ray Emission (PIXE). Rainwater samples were collected using a wet-only sampler and samples were analyzed for pH and ionic composition, which was determined using ionic chromatography (IC). Natural sources dominated the aerosol mass during the wet season, when it was predominantly of natural biogenic origin mostly in the coarse mode, which comprised up to 81% of PM10. Biogenic aerosol from both primary emissions and secondary organic aerosol dominates the fine mode in the wet season, with very low concentrations (average 2.2 mu g m(-3)). Soil dust was responsible for a minor fraction of the aerosol mass (less than 17%). Sudden increases in the concentration of elements as Al, Ti and Fe were also observed, both in fine and coarse mode (mostly during the April-may months), which we attribute to episodes of Saharan dust transport. During the dry periods, a significant contribution to the fine aerosols loading was observed, due to the large-scale transport of smoke from biomass burning in other portions of the Amazon basin. This contribution is associated with the enhancement of the concentration of S, K, Zn and BCE. Chlorine, which is commonly associated to sea salt and also to biomass burning emissions, presented higher concentration not only during the dry season but also for the April-June months, due to the establishment of more favorable meteorological conditions to the transport of Atlantic air masses to Central Amazonia. The chemical composition of rainwater was similar to those ones observed in other remote sites in tropical forests. The volume-weighted mean (VWM) pH was 4.90. The most important contribution to acidity was from weak organic acids. The organic acidity was predominantly associated with the presence of acetic acid instead of formic acid, which is more often observed in pristine tropical areas. Wet deposition rates for major species did not differ significantly between dry and wet season, except for NH4+, citrate and acetate, which had smaller deposition rates during dry season. While biomass burning emissions were clearly identified in the aerosol component, it did not present a clear signature in rainwater. The biogenic component and the long-range transport of sea salt were observed both in aerosols and rainwater composition. The results shown here indicate that in Central Amazonia it is still possible to observe quite pristine atmospheric conditions, relatively free of anthropogenic influences.

Glacier mass balance reconstruction by sublimation induced enrichment of chemical species on Cerro Tapado (Chilean Andes)

A 36 m long ice core down to bedrock from the Cerro Tapado glacier (5536 m a.s.l, 30°08' S, 69°55' W) was analyzed to reconstruct past climatic conditions for Northern Chile. Because of the marked seasonality in the precipitation (short wet winter and extended dry summer periods) in this region, major snow ablation and related post-depositional processes occur on the glacier surface during summer periods. They include predominantly sublimation and dry deposition. Assuming that, like measured during the field campaign, the enrichment of chloride was always related to sublimation, the chemical record along the ice core may be applied to reconstruct the history of such secondary processes linked to the past climatic conditions over northern Chile. For the time period 1962–1999, a mean annual net accumulation of 316 mm water equivalent (weq) and 327 mm weq loss by sublimation was deduced by this method. This corresponds to an initial total annual accumulation of 539 mm weq. The annual variability of the accumulation and sublimation is related with the Southern Oscillation Index (SOI): higher net-accumulation during El-Niño years and more sublimation during La Niña years. The deepest part of the ice record shows a time discontinuity; with an ice body deposited under different climatic conditions: 290 mm higher precipitation but with reduced seasonal distribution (+470 mm in winter and –180 mm in summer) and –3°C lower mean annual temperature. Unfortunately, its age is unknown. The comparison with regional proxy data however let us conclude that the glacier buildup did most likely occur after the dry mid-Holocene.

Chemical and Sr isotopic compositions and timing of carbonate mineral precipitation, ODP Leg 115

The strontium isotope ratios of authigenic carbonates from Indian Ocean sea-floor basalts have been used to determine the timing of carbonate mineral precipitation and fluid flow. The samples include calcites from 57.2 Ma crust from Ocean Drilling Project (ODP) Site 715, and calcites, aragonites, and siderites from 63.7 Ma crust from ODP Site 707. At Site 715, calcite precipitation may have begun at any time after the basalts cooled, and it continued until approximately 31 Ma, or 26 m.y. after basalt eruption. At Site 707, aragonite and siderite did not begin to precipitate until about 36 Ma, almost 30 m.y. after basalt eruption, and continued to precipitate until at least 30 and 28 Ma, respectively. Calcite precipitation began at approximately 32 Ma and continued until 22 Ma. These ages suggest that vein mineral deposition and low-temperature fluid circulation in the ocean crust may continue for much longer periods of time than previously observed.

Chemical composition of interstitial solutions from sediments of DSDP Legs 6-8, 11, 12, 14, 15, and 22

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments. Pelagic clays and slowly deposited (<1 cm/1000 yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters. In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/1000 yr the changes chiefly involve gains of Ca(2+) and Sr(2+) and losses of Mg(2+) which balance the Ca(2+) enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr(2+) may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg(2+) for Ca(2+) during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca(2+) and Sr(2+) enrichment is again characteristic, but Mg(2+) losses exceed Ca(2+) gains with the excess being balanced by SO4(post staggered 2-) losses. The data indicate that the reactions are similar to those noted above, except that the Ca(2+) released is not kept in solution but is precipitated by the HCO3(post staggered -) produced in SO4(post staggered 2-) reduction. In both these types of pore waters Na(+) is usually conservative, but K(+) depletions are frequent. In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na(+), Si and CO2, and slight enhancement in Cl(-). The changes are attributed to exchange of Na(+) for Ca(2+) in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity. Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4(post staggered 2-), strong HCO3(post staggered -) enrichment, formation of NH4(post staggered +), and methane synthesis from H2 and CO2 once SO4(post staggered 2-) is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca(2+) depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl- remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl- are observed in some sediments adjacent to continents.

Chemical and isotopic compositions of groundwaters in the Badain Jaran Desert, Northern China

Despite its extreme aridity the Badain Jaran Desert is rich in groundwater. In the southeastern part of this desert it is characterized by coexistence of high megadunes and a great number of lakes. Deuterium and oxygen 18 isotope compositions as well as hydrochemistry of groundwater, lake water, soil water and river water were investigated in detail to gain an insight into their relationships and the origin of the groundwater. The results show that the groundwater and the lake water are genetically related, but unrelated to local precipitation and the leakage of Heine River at the northern slope of the Qilian mountain. dD and d18O values of deep soil water (deeper than 40 cm) and groundwater plot on the same evaporation line E11, which shows that they have the same recharge source. The point of intersection between E11 and LMWL suggests that the groundwater originates from a water resource, which has a weighted mean value that is lighter by some 6 per mil d18O than local precipitation in Badain Jaran Desert. 3H data of water samples show that the groundwater in the Badain Jaran Desert originates from water recharged after the nuclear test. The deep fault zone underground maybe a water circulation channel based on helium analysis of groundwater. The result has guiding significance to rational exploitation and utilization of the local groundwater.

Description and chemical composition of ferromanganese deposits from Oneida Lake, New York

Saucer-shaped iron-manganese crusts occur adjacent to gravel shoal areas in Oneida lake in central New York. The crusts usually have a crude concentric banding owing to an alternation of orange, iron-rich layers and black, iron-poor layers. Materials from both types of layers are x-ray amorphous. The Oneida lake crusts, like most other freshwater manganese nodules, contain about the same Mn concentration as marine manganese nodules, but are usually higher in Fe and lower in trace metals than their marine equivalents. Although Fe and Mn may be precipitating directly from the lake water, it is more likely that the oxidate crusts are the result of precipitation of Fe and Mn when reduced sediment pore water comes in contact with well oxygenated bottom waters. Organisms, particularly bacteria, may play a role in the formation of the crusts, but to date no evidence of this has been found.

Chemical composition and description of a ferromanganese crust, sample 89D, obtained during R/V Capricorne cruise ARCANTE 1

A manganese oxide encrustation (2.5 kg) was dredged, in an island arc setting, downslope of Bertrand bank, a seamount culminating at 70-m depth and located NNE of Grande-Terre, Guadeloupe, and SE of Antigua, West Indies. A thorough texturai analysis indicated a rhythmic precipitation and growth polarity as well as mineralogical ( 10 A tektomanganate) and geochemical (low concentrations of Ni, Cu, Co, Zn, Pb and REE) criteria, point to a submarine hydrothermal origin for most of the sample. The crust was coated with a fine ferromanganese oxide cortex deposited iii a "normal" oceanic environment; it also included micritic fillings, a main pyroclastic zone near the top of the crust, and a Mg-Al sulphate deposit. Planktonic foraminifera coeval with the precipitation of the manganese oxide indicate an age of ca. 3 m. y. (upper Pliocene); i.e., more than 20 m. y. after the cessation of the volcanic activity of the Lesser Antilles outer arc that was responsible for the buildup of the Bertrand seamount. Furthermore, the genesis of the crust is not linked to the activity of the contemporaneous inner arc (Miocene to Present), particularly of its nearmost segment (Basse Terre, Guadeloupe-Montserrat) located about 50 km to the West. The authors suggest that the manganese oxide is the result of convective circulation of sea water through a faulted system occurring in an area of intense seismic activity. The remobilization of chemical elements (Mn, S, etc.) within the seamount volcanic core bas probably affected a substratum that was still hydrothermally altered during the previous volcanic activity of the outer arc. The authors insist on the interest in using texturai analysis for Fe/Mn oxide investigations.

Piggery pond sludge as a nitrogen source for crops - 2. Assay of wet and stockpiled piggery pond sludge by successive cereal crops or direct measurement of soil available N

The appropriate use of wastes is a significant issue for the pig industry due to increasing pressure from regulatory authorities to protect the environment from pollution. Nitrogen contained in piggery pond sludge ( PPS) is a potential source of supplementary nutrient for crop production. Nitrogen contribution following the application of PPS to soil was obtained from 2 field experiments on the Darling Downs in southern Queensland on contrasting soil types, a cracking clay ( Vertosol) and a hardsetting sandy loam (Sodosol), and related to potentially mineralisable N from laboratory incubations conducted under controlled conditions and NO3- accumulation in the field. Piggery pond sludge was applied as-collected ( wet PPS) and following stockpiling to dry ( stockpiled PPS). Soil NO3- levels increased with increased application rates of wet and stockpiled PPS. Supplementary N supply from PPS estimated by fertiliser equivalence was generally unsatisfactory due to poor precision with this method, and also due to a high level of NO3- in the clay soil before the first assay crop. Also low recoveries of N by subsequent sorghum ( Sorghum bicolor) and wheat ( Triticum aestivum) assay crops at the 2 sites due to low in-crop rainfall in 1999 resulted in low apparent N availability. Over all, 29% ( range 12 - 47%) of total N from the wet PPS and 19% ( range 0 - 50%) from the stockpiled PPS were estimated to be plant-available N during the assay period. The high concentration of NO3- for the wet PPS application on sandy soil after the first assay crop ( 1998 barley, Hordeum vulgare) suggests that leaching of NO3- could be of concern when high rates of wet PPS are applied before infrequent periods of high precipitation, due primarily to the mineral N contained in wet PPS. Low yields, grain protein concentrations, and crop N uptake of the sorghum crop following the barley crop grown on the clay soil demonstrated a low residual value of N applied in PPS. NO3- in the sandy soil before sowing accounted for 79% of the variation in plant N uptake and was a better index than anaerobically mineralisable N ( 19% of variation explained). In clay soil, better prediction of crop N uptake was obtained when both anaerobically mineralisable N (39% of variation explained) and soil pro. le NO3- were used in combination (R-2 = 0.49).