Characterisation of atmospheric single particles in industrial and regional background environments using aerosol time of flight mass spectrometry

The composition of atmospheric particles is an important factor in determining their impact on climate and health. In this study, an aerosol time-of-flight mass spectrometer (ATOFMS) was used to measure the chemical composition of ambient single particles at two contrasting locations – an industrial site in Dunkirk, France and a regional background site in Corsica. The ATOFMS data were combined with meteorological information and other particle measurements to determine the various sources of the particles observed at the sites. The particle classes detected in Dunkirk included carbonaceous species from fossil fuel combustion and biomass burning, metal-containing types from local industries and seasalt. Highest particle number concentrations and mass concentrations of PM2.5, black carbon, organics, nitrate, ammonium and several metallic species (Fe, Mn, Pb, Zn) were found during periods heavily influenced by local industry. Particles from a ferromanganese alloy manufacturing facility were identified by comparing ambient ATOFMS data with single particle mass spectra from industrial chimney filters and ores. Particles from a steelworks were identified based on comparison of the ambient data with previous studies. Based on these comparisons, the steelworks was identified as the dominant emitter of Fe-rich particles, while the ferromanganese alloy facility emitted Mn-rich particles. In Corsica, regional transport of carbonaceous particles from biomass burning and fossil fuel combustion was identified as the major source of particles in the Mediterranean background aerosol. Throughout the campaign the site was influenced by air masses altering the composition of particles detected. During North Atlantic air masses the site was heavily influenced by fresh sea salt. Regional stagnation was the most common type of air mass regime throughout the campaign and resulted in the accumulation of carbonaceous particles during certain periods. Mass concentrations were estimated for ATOFMS particle classes, and good agreement was found between the major carbonaceous classes and other quantitative measurements. Overall the results of this work serve to highlight the excellent ability of the ATOFMS technique in providing source-specific composition and mixing state information on atmospheric particles at high time resolution.

Geochemistry of the Japan Trench sediments at DSDP Legs 56-57 Holes

The main objective of this investigation was to study distribution of main chemical constituents and several minor elements in sediment sections drilled during DSDP Legs 56 and 57 in the Japan Trench, in order to infer geochemical features of different lithologic types of sediments, and to find out how the geochemistry is associated with major lithologic constituents, such as terrigenous detrital matter, clay, volcanic ash, and biogenic particles. The geochemical data may help to indicate the nature of the sediments and to interpret sedimentation processes. The analyzed samples seem to be representative of most lithologic units, sub-units, and sediment types drilled at all sites on both legs, except for some shallow-water deposits at Sites 438 and 439. We analyzed bulk-sediment composition by X-ray fluorescence (Kuzmina and Turanskaya) and routine wet-chemical methods (Mikhailov); amorphous SiO2, extracted in a boiling sodium carbonate solution (Analythical Laboratory, P. P. Shirshov Institute of Oceanology); Cr, Zn, Cu, Ni, Co, and Al by atomic absorption (Gordeev); and Sn, Pb, Zn, Cu, Ni, Co, Cr, V, B, and Ag by quantitative spectrographic analyses in both bulk samples and granulometric fractions (Mikhailov). In addition, Fe, Ti, Mn, and CaCO3 have been determined in selected samples by routine wet-chemical methods (Analytical Laboratory, P. P. Shirshov Institute of Oceanology). Murdmaa was responsible for interpretation of the results.

Contents of metal cations exchange capacity of ore minerals in ferromanganese micronodules from the Atlantic, Indian and Pacific Oceans

Results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules from diverse bioproductive zones of the World Ocean were considered. It was found that sorption behavior of these minerals was similar to that of ore minerals from ferromanganese nodules and low-temperature hydrothermal crusts. The exchange complex of minerals in the micronodules includes the major (Na**+, K**+, Ca**2+, Mg**2+, and Mn**2+) and subordinate (Ni**2+, Cu**2+, Co**2+, Pb**2+, and others) cations. Reactivity of theses cations increases from Pb**2+ and Co**2+ to Na**+ and Ca**2+. Exchange capacity of micronodule minerals increases from alkali to heavy metal cations. Capacity of iron and manganese minerals in oceanic micronodules increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite ~= Fe-vernadite + Mn-feroxyhyte. Obtained data supplement available information on ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in redistribution of metal cations at the bottom water - sediment interface during micronodule formation and growth.

Raw and normalized X-ray fluorescence (XRF) scannings of IODP Expedition 321, Site U1338

We used X-ray fluorescence (XRF) scanning on Site U1338 sediments from Integrated Ocean Drilling Program Expedition 321 to measure sediment geochemical compositions at 2.5 cm resolution for the 450 m of the Site U1338 spliced sediment column. This spatial resolution is equivalent to ~2 k.y. age sampling in the 0-5 Ma section and ~1 k.y. resolution from 5 to 17 Ma. Here we report the data and describe data acquisition conditions to measure Al, Si, K, Ca, Ti, Fe, Mn, and Ba in the solid phase. We also describe a method to convert the data from volume-based raw XRF scan data to a normalized mass measurement ready for calibration by other geochemical methods. Both the raw and normalized data are reported along the Site U1338 splice.

(Table 1) Nd isotope ratios of ODP Leg 208 samples

We present new Nd isotope records from Walvis Ridge Ocean Drilling Program (ODP) sites 1262-1264 (southeastern Atlantic) spanning the past 24 Ma to investigate the Neogene evolution of Atlantic thermohaline circulation. The new data indicate that deepwater epsilon-Nd(t) values from ODP Site 1262 decrease from -11.0 at 10.6 Ma to -12.5 by 7.3 Ma. This decrease parallels the Nd isotope trends contained in Fe-Mn crust records from the northwestern Atlantic; however, the shift at ODP Site 1262 (4755 m water depth) occurred up to ~6 Ma earlier than the corresponding changes in crust records from the Atlantic and earlier than any Atlantic site shallower than 2700 m paleowater depth. Recent interpretations of the rapid decrease in Fe-Mn crust Nd epsilon-Nd(t)ss values invoke changes in weathering inputs to the Labrador Sea region rather than a fundamental change in deepwater convection in the Labrador Sea. However, the new evidence for significant depth stratification of the Nd isotope signal in the southeastern Atlantic between 10.6 and 7.3 Ma suggests that the onset of deepwater convection in the Labrador Sea may have played a role in the deepwater decrease in Nd isotopic composition. Climatic conditions during the middle to late Miocene likely favored an increase in the importance of glacially induced mechanical weathering, while at the same time promoting deep convection in the Labrador Sea.

Nd/Ca ratios in plankton-towed and core top foraminifera

Planktic foraminifera have been used as recorders of the neodymium (Nd) isotopic composition of seawater, although there is still controversy over the precise provenance of the Nd signal. We present an extensive, multispecific plankton tow Nd/Ca data set from several geographic locations (SE Atlantic, NE Atlantic, Norwegian Sea, and western Mediterranean), together with core top samples from the Mediterranean region. The range of Nd/Ca ratios in plankton-towed foraminifera, cleaned only of organic material, from all regions (0.01-0.7 µmol/mol), is similar to previously published analyses of sedimentary foraminifera cleaned using both oxidative and reductive steps, with distribution coefficients (Kd) ranging between 4 and 302. For the Mediterranean, where core top and plankton tow data are both available, the range for plankton tows (0.05-0.7 µmol/mol) is essentially identical to that for the core tops (0.1-0.5 µmol/mol). Readsorption of Nd during cleaning is ruled out by the fact that the plankton tow samples underwent only an oxidative cleaning process. We find a relationship between manganese (Mn) and Nd in plankton tow samples that is mirrored by a similar correlation in core top samples. This relationship suggests that Fe-Mn coatings are of negligible importance to the Nd budgets of foraminifera as the Nd/Mn ratio it implies is over an order of magnitude greater than that seen in other Fe-Mn oxide phases. Rather, since both plankton tows and core tops present a similar behavior, the Nd/Mn relationship must originate in the upper water column. The data are consistent with the acquisition of Nd and Mn from the water column by binding to organic material and the fact that intratest organic material is shielded from both aggressive cleaning and diagenetic processes. Collectively, the results help to explain two abiding puzzles about Nd in sedimentary planktic foraminifera: their high REE contents and the fact that they record a surface water Nd isotopic signal, regardless of the cleaning procedure used.

(Table 3, page 309) Mercury content of concretions from Grand Lake (GL) and Ship Harbour Lake (SH), Nova Scotia and Mosque Lake (ML), Ontario

Ferromanganese concretions from Grand Lake and Ship Harbour Lake in Nova Scotia and Mosque Lake in Ontario are most common in water 0.5 to 2 m deep. X-ray diffraction studies show the ferromanganese portions of the concretions to he amorphous. Petrographic and electron probe studies of the ferromanganese material reveal chemical banding of iron and manganese. Bulk chemical analyses indicate that the Fe:Mn ratios of concretions from different sites within a single lake are similar, whereas concretions from different lakes have characteristic Fe:Mn ratios. Trace element concs are different in different lakes and are generally several orders of magnitude less than those of oceanic nodules.

Mineralogical, geochemical and magnetic signatures of surface sediments from the Canadian Beaufort Shelf and Amundsen Gulf (Canadian Arctic)

Mineralogical, geochemical, magnetic, and siliciclastic grain-size signatures of 34 surface sediment samples from the Mackenzie-Beaufort Sea Slope and Amundsen Gulf were studied in order to better constrain the redox status, detrital particle provenance, and sediment dynamics in the western Canadian Arctic. Redox-sensitive elements (Mn, Fe, V, Cr, Zn) indicate that modern sedimentary deposition within the Mackenzie-Beaufort Sea Slope and Amundsen Gulf took place under oxic bottom-water conditions, with more turbulent mixing conditions and thus a well-oxygenated water column prevailing within the Amundsen Gulf. The analytical data obtained, combined with multivariate statistical (notably, principal component and fuzzy c-means clustering analyses) and spatial analyses, allowed the division of the study area into four provinces with distinct sedimentary compositions: (1) the Mackenzie Trough-Canadian Beaufort Shelf with high phyllosilicate-Fe oxide-magnetite and Al-K-Ti-Fe-Cr-V-Zn-P contents; (2) Southwestern Banks Island, characterized by high dolomite-K-feldspar and Ca-Mg-LOI contents; (3) the Central Amundsen Gulf, a transitional zone typified by intermediate phyllosilicate-magnetite-K-feldspar-dolomite and Al-K-Ti-Fe-Mn-V-Zn-Sr-Ca-Mg-LOI contents; and (4) mud volcanoes on the Canadian Beaufort Shelf distinguished by poorly sorted coarse-silt with high quartz-plagioclase-authigenic carbonate and Si-Zr contents, as well as high magnetic susceptibility. Our results also confirm that the present-day sedimentary dynamics on the Canadian Beaufort Shelf is mainly controlled by sediment supply from the Mackenzie River. Overall, these insights provide a basis for future studies using mineralogical, geochemical, and magnetic signatures of Canadian Arctic sediments in order to reconstruct past variations in sediment inputs and transport pathways related to late Quaternary climate and oceanographic changes.

Analytical data as related to sediment types and water depth, Adriatic Sea

A preliminary set of heavy metal analyses from surface sediment samples covering the whole Adriatic Basin is presented, and their significance in terms of pollution is discussed. The core samples were analysed for Fe, Mn, Cr, Cu, Ni, Pb, Zn, P, organic carbon, Ca- and Mg-carbonate, and their mineralogical composition and grain size distribution were determined. All heavy metal concentrations found can be attributed to natural sedimentological processes and are not necessarily to be interpreted as indications of pollution.

Major element compositions, minerals and trace elements at DSDP Leg 67 Holes

Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 18 samples of volcanic rocks from the Guatemala Trench area (Deep Sea Drilling Project Leg 67). Typical fresh oceanic tholeiites occur in the trench itself (Hole 500) and in its immediate vicinity on the Cocos Plate (Site 495). Several samples (often reworked) of "spilitic" oceanic tholeiites are also described from the Trench: their mineralogy (greenschist facies association - actinolite + plagioclase + chlorite) and geochemistry (alteration, sometimes linked to manganese and zinc mineralization) are shown to result from high-temperature (300°-475°C) hydrothermal sea water-basalt interactions. The samples studied are depleted in light rare-earth elements (LREE), with the exception of the slightly LREE-enriched basalts from Hole 500. The occurrence of such different oceanic tholeiites in the same area is problematic. Volcanic rocks from the Guatemala continental slope (Hole 494A) are described as greenschist facies metabasites (actinolite + epidote + chlorite + plagioclase + calcite + quartz), mineralogically different from the spilites exposed on the Costa Rica coastal range (Nicoya Peninsula). Their primary magmatic affinity is uncertain: clinopyroxene and plagioclase compositions, together with titanium and other hygromagmaphile element contents, support an "active margin" affinity. The LREE-depleted patterns encountered in the present case, however, are not frequently found in orogenic samples but are typical of many oceanic tholeiites.

Mineralogy of sediments at DSDP Leg 67 Hole

Seven sites were drilled during Leg 67 along a transect across the Middle America Trench off Guatemala: four (Sites 494, 496, 497, and 498) on continental slope, two (Sites 499 and 500) on Trench floor, and one (Site 495) on the Cocos Plate. We studied the mineralogy of sediments from Sites 494, 495, 496, 499, and 500. Our objective was to investigate the origin and source of separate minerals and mineral assemblages, giving special attention to the influence of the alteration of basalts on the sediment mineralogy, which we expected to be particularly important in layers just above oceanic basement.

Evolution of neodymium isotopic signature of seawater during the Late Cretaceous: Implications for intermediate and deep circulation

Neodymium isotopic compositions (εNd) have been largely used for the last fifty years as a tracer of past ocean circulation, and more intensively during the last decade to investigate ocean circulation during the Cretaceous period. Despite a growing set of data, circulation patterns still remain unclear during this period. In particular, the identification of the deep-water masses and their spatial extension within the different oceanic basins are poorly constrained. In this study we present new deep-water εNd data inferred from the Nd isotope composition of fish remains and Fe-Mn oxyhydroxide coatings on foraminifera tests, along with new εNd data of residual (partly detrital) fraction recovered from DSDP sites 152 (Nicaraguan Rise), 258 (Naturaliste Plateau), 323 (Bellinghausen Abyssal Plain), and ODP sites 690 (Maud Rise) and 700 (East Georgia Basin, South Atlantic). The presence of abundant authigenic minerals in the sediments at sites 152 and 690 detected by XRD analyses may explain both middle rare earth element enrichments in the spectra of the residual fraction and the evolution of residual fraction εNd that mirror that of the bottom waters at the two sites. The results point towards a close correspondence between the bottom water εNd values of sites 258 and 700 from the late Turonian to the Santonian. Since the deep-water Nd isotope values at these two sites are also similar to those at other proto-Indian sites, we propose the existence of a common intermediate to deep-water water mass as early as the mid-Cretaceous. The water mass would have extended from the central part of the South Atlantic to the eastern part of proto-Indian ocean sites, beyond the Kerguelen Plateau. Furthermore, data from south and north of the Rio Grande Rise-Walvis Ridge complex (sites 700 and 530) are indistinguishable from the Turonian to Campanian, suggesting a common water mass since the Turonian at least. This view is supported by a reconstruction of the Rio Grande Rise-Walvis Ridge complex during the Turonian, highlighting the likely existence of a deep breach between the Rio Grande Rise and the proto-Walvis Ridge at that time. Thus deep-water circulation may have been possible between the different austral basins as early as the Turonian, despite the presence of potential oceanic barriers. Comparison of new seawater and residue εNd data on Nicaraguan Rise suggest a westward circulation of intermediate waters through the Caribbean Seaway during the Maastrichtian and Paleocene from the North Atlantic to the Pacific. This westward circulation reduced the Pacific water influence in the Atlantic, and was likely responsible for more uniform, less radiogenic εNd values in the North Atlantic after 80 Ma. Additionally, our data document an increasing trend observed in several oceanic basins during the Maastrichtian and the Paleocene, which is more pronounced in the North Pacific. Although the origin of this increase still remains unclear, it might be explained by an increase in the contribution of radiogenic material to upper ocean waters in the northern Pacific. By sinking to depth, these waters may have redistributed to some extent more radiogenic signatures to other ocean basins through deep-water exchanges.

CRESCIMENTO INICIAL DE ACÁCIA-NEGRA COM VERMICOMPOSTOS DE DIFERENTES RESÍDUOS AGROINDUSTRIAIS

A utilização de vermicompostos de diferentes resíduos agroindustriais na produção de mudas de acácianegra pode ser uma alternativa de reutilização de resíduos e aumentar a produção de mudas. Assim, os objetivos deste trabalho foram avaliar o crescimento e a concentração de nutrientes em mudas de acácianegra, cultivadas em substratos com diferentes vermicompostos de resíduos orgânicos agroindustriais. Instalou-se em casa de vegetação 11 diferentes tratamentos: T1) vermicomposto de esterco bovino (EB); T2) vermicomposto de esterco ovino (EO); T3) vermicomposto de lodo de parbolização de arroz (LP); T4) tratamento controle (sem adubação); T5) tratamento controle com adução mineral (NPK); T6) mistura de EB e LP; T7) mistura de EO e LP; T8) mistura de EB e vermicomposto de resíduos de alimentos (RA); T9) mistura de EO e RA; T10) mistura de EB e vermicomposto de resíduos de frutas (RF); T11) mistura de EO e RF. Após 180 dias de cultivo em recipiente com capacidade de cinco litros, foram analisadas a massa seca e a concentração de nutrientes na parte aérea da acácia-negra, e a concentração de nutrientes no solo, após o cultivo. A adição do esterco bovino, bem como a mistura de esterco bovino e resíduos alimentícios favoreceram o incremento de matéria seca das plantas de acácia-negra. Os resultados mostraram que as concentrações de nutrientes nas plantas, com exceção de Fe e Mn, variaram com adição de vermicompostos no solo. Os tratamentos T3 e T6 elevaram as concentrações em P, N, Zn de Cu nas folhas de acácia-negra. Além disso, a adição dos vermicompostos ao solo aumentou a disponibilidade de nutrientes para as plantas, mesmo após o cultivo, especialmente com relação ao fósforo, potássio e magnésio, sendo uma alternativa viável e eficaz na produção de mudas, podendo substituir a utilização de adubação mineral.

AVALIAÇÃO COMPARATIVA DO ESTADO NUTRICIONAL DE MUDAS DE BARU ( Dipteryx alata )

Para o sucesso de um processo de revegetação, além de melhorar as condições edáficas da área, deve-se dispor de mudas de boa qualidade, o que pode ser avaliado pelo estado nutricional. Neste trabalho, avaliaramse os teores foliares de N, P, K, Ca, Mg, S, B, Cu, Fe, Mn e Zn de mudas de Dipteryx alata produzidas a pleno sol ou em cultivo protegido (30% de sombreamento), utilizando como substrato solo degradado, condicionado ou não com resíduo orgânico (32 t ha-1 macrófitas) e com diferentes doses de fósforo (0, 100, 200 e 300 mg dm-3 P2O5), comparativamente à mudas e parte aérea de plantas adultas, coletadas em campo. A cada coleta de folhas em campo, o solo foi coletado e analisado para P, MO, pH, K, Ca, Mg, H+Al, SB e CTC. A mesma análise foi realizada nas unidades experimentais, ao final do experimento. Os resultados mostram que o Dipteryx alata é pouco exigente em P, que os teores foliares, nas mudas de campo, são superiores às plantas adultas em N, P, K e S e inferiores para Ca e que o estádio de desenvolvimento da planta não influenciou os teores foliares de Mg, B, Cu, Fe, Mn e Zn. O resíduo orgânico não foi suficiente para fornecer o N necessário às mudas produzidas. O cultivo a pleno sol propiciou maiores teores foliares de N, P, Ca, Mg, B, Cu, Fe e Mn. Teores foliares de N, P, K, Ca, B, Fe e Zn foram superiores na presença de resíduo orgânico.

Maize inbreds from different heterotic groups as favorable sources for increased potential bioavailability of magnesium, iron, manganese and zinc

Malnutrition, as a global problem, is mainly caused by low level of mineral elements in staple food (deficient soil). Biofortification is based on selection of genotypes with enhanced concentration of mineral elements in grain, as well as decreased concentration of substances which interfere bioavailability of mineral elements in gut (like phytic acid), and increased content of substances that increase availability (such as β-carotene). The experiment with 51 maize ( Zea mays L.) inbred lines with different heterotic background was set up in order to evaluate chemical composition of grain and to determine the relations between phytic acid (PA), β-carotene, and mineral elements: Mg, Fe, Mn, and Zn. The highest average phytate, β-carotene, Fe, and Mn content was found in grain of inbreds from Lancaster heterotic group. The highest content of Mg was in grain of Independent source and Zn in grain of BSSS group. Increased level of Fe and Mn in Lancaster lines could be partially affected by higher PA content in grain, while increased β-carotene content could improve Mn and Zn availability from grain of BSSS genotypes and Mg availability from Lancaster inbreds. It is important to underline that PA reduction is followed by Zn content increase in grain of Lancaster heterotic group, as well as that variations in Mg, Fe, and Mn contents are independent on PA status in inbreds from Independent source, indicating that the genotypes with higher Mg, Fe and Mn status from this group could serve as favorable source for improved Mg, Fe, and Mn absorption.