The environmental processes and conditions controlling productivity and organic matter (OM) accumulation/preservation as well as bottom–water redox conditions in the lower black shale (LBS) and upper black shale (UBS) members of the Devonian-Mississippian (D–M) Bakken Formation were evaluated utilizing trace metal (TM) concentrations, degree of pyritization (DOPT), enrichment factors (EF) of TMs, bi–metal ratios (V/Cr, V/(V+Ni), Ni/Co, U/Th), total sulfur (ST) vs. iron (Fe), total organic carbon (TOC), carbon–sulfur–iron relationships (C–S–Fe), as well as Mo–TOC and Mo EF–U EF relationships. High-resolution (1- to 3-cm scale) chemostratigraphic records were generated for twelve drill cores, four of which closely flank the N–S-trending axis of the Nesson Anticline, proximal to the center of the Williston Basin in northwest North Dakota, USA. Furthermore, five of the twelve drill cores were selected (sample selection was based on down–core spacing and TM concentrations) for petrographic and Rock-Eval analysis to assess variations in kerogen type, quantity, quality, and thermal maturity (based on solid bitumen reflectance (%SBRo), vitrinite reflectance equivalence (%VRE), Rock–Eval Tmax–derived vitrinite reflectance (%Ro)) from immature to condensate, wet gas hydrocarbon generation windows. Degree of pyritization (DOPT) values (0.25 to 1.0) indicate that bottom waters were frequently dysoxic (> 60%) with intermittent aerobic and anoxic/euxinic conditions which is in agreement with C–S–Fe and total ST vs. Fe assessments of paleoredox conditions and sedimentological evidence. Furthermore, using published Mo–TOC relationships from modern anoxic-euxinic basins, it is estimated that renewal time of the sub-chemoclinal water mass during accumulation of the LBS and UBS approximated 10 and 30 yrs., respectively. Agreement is also seen between Mo/TOC and Mo EF/U EF where both suggest the Bakken shales were deposited under relatively unrestricted water mass conditions resulting in consistent renewal of TMs into the basin. However, bi–metal ratios suggest > 80% of samples were deposited under suboxic to anoxic/euxinic conditions. Trace metal concentrations for the Bakken Fm. show considerable range for Co (0–10324 ppm), Mo (0–2018 ppm), Ni (0–1574 ppm), U (0–1604 ppm), and V (0–3194 ppm), and bi–metal ratios for the Bakken Fm. are up to 5x greater than those reported for other D–M black shale formations. The Bakken black shales represent a unique sedimentary system where the EF of various TMs such as Cu (6.2–7.7), Mo (219.7–237.8), Ni (9.4–10.2), U (20.6–29.3), V (9.9–14.2), and Zn (10.4–12.2) as well as total organic carbon contents (LBS = 10.80 and UBS = 11.80 avg. wt.%) are considerably higher than other Devonian–Mississippian black shales. In this study, raw distributions of elemental concentrations combined with bivariate and principal component analysis (PCA) were used to elucidate the processes that could have contributed to the high EF of TMs in the Bakken shales. Total organic carbon shares heavier PCA component loadings (>0.445) and stronger correlation coefficients (r) with Cu, Mo, Ni, U, V, and Zn rather than with pyrite-associated (As, Co, Fe, and S) elements, suggesting that TOC played a primary role in the scavenging and accumulation of TMs in the sediments. Reducing conditions within bottom waters or sediment pore waters may have accelerated the accumulation of redox-sensitive Cu, Mo, Ni, V, and Zn introduced into the sediments via primarily an organic matter (OM) detritus host and most likely played a secondary role in the enrichment of TMs. The high EF of TMs observed in the Bakken shales may be the result of the frequent resupply of TMs into basin waters, enhanced primary productivity that is necessary in scavenging TMs from the water column, the presence of H2S within sediment pore or bottom waters, or possibly secondary processes associated with basin-wide fluid and hydrocarbon migration. Factors controlling TM accumulation during time of deposition (e.g., TM availability, bottom-water redox conditions, adsorption onto organic matter) and during diagenesis and catagenesis (e.g., alteration and break down of organic matter, movement of fluid hydrocarbons or other basinal fluids) likely contribute to the lack of agreement between redox proxies, and subsequently, the lack of applicability of bi–metal ratios (i.e., V/Cr, V/(V+Ni), Ni/Co, U/Th) in assessing bottom–water conditions for the Bakken shales. Solid bitumen (SB), a secondary organic matter formed as a residue after hydrocarbon generation (through either sufficient thermal maturation or microbial degradation) and expulsion, is primarily dispersed within the mineral matrix and increases in quantity with increasing thermal maturity. Rock-Eval II and HAWK analyzers were used to measure and estimate the hydrogen index (HI; avg. 201 mg HC/g TOC), oxygen index (OI; avg. 7mg CO2/g TOC), S1 (free hydrocarbons; avg. 8.0 mg HC/g rock), S2 (hydrocarbons generated after cracking kerogen; avg. 24.3 mg HC/g rock), and %Ro (0.60–1.03%; estimated from Tmax). The HI and OI values are calculated from TOC as well as S2 and S3 (oxygen bonded to hydrocarbons). Plots of HI vs. Tmax (ºC) and HI vs. OI as well as S2 vs. S3 ratio were utilized to determine the type of kerogen, primary OM that is insoluble in organic solvents. However, these relationships are not in agreement with kerogen typing based on petrographic observations, where samples from more thermally mature cores plot as Type III (vitrinite) kerogen instead of observed Type I/II (marine algae) kerogen. This is largely due to the abundant presence of SB in the more thermally mature section of the Bakken (Rock-Eval Ro = 0.83–1.03%) as SB is known to have a lower HI content than Type II kerogen. Petrographic evidence shows greater abundance of alginite and amorphous organic matter (AOM or bituminite) in the thermally less mature (Rock-Eval Ro = 0.60–0.83%) section of the Bakken compared to the greater abundance of dispersed SB in the more thermally mature section where AOM is absent. Early research on the Bakken Fm. reported lower than expected vitrinite reflectance values attributed to vitrinite “suppression". The overall lack of vitrinite and abundance of solid bitumen in these shales suggests that these early attempts likely reported solid bitumen reflectance rather than vitrinite reflectance. More recent attempts to assess the thermal maturity of the Bakken Fm. black shales have measured and converted SBRo to vitrinite reflectance equivalent (VRE). However, samples selected for SBRo by some previous workers have included heterogenous, granular as well as high reflecting SB samples, which introduce error in the measurements. As such, reported reflectance values are most likely lower than they would be if smooth, homogenous solid bitumen with no inclusions were measured. For this project, smooth and homogenous SB was measured to produce consistent and reliable VRE values to assess the thermal maturity gradient from the Bakken Fm. basin margins to the depocenter. Blue-light fluorescence petrography was done to support thermal maturity assessments. Results from SBRo, Rock-Eval Ro, VRE, and blue-light fluorescence observations suggest that cores from the current study range from early oil window into condensate, wet gas.

In recent years, the celebration activities of various types of folk-custom festivals in Taiwan have already been getting more and more attention from civilians. Festivities throughout the whole island are traditionally accompanied by loud and brightly colored firework displays. Among these activities, the firework display during the Chinese Lantern Festival in Kaohsiung City is one of the largest festivals in Taiwan every year. Therefore, it is important to investigate the influences of firework displays on ambient air quality during the Chinese Lantern Festival in Kaohsiung City. Field measurement of ambient gaseous pollutants and particulate matter (PM) was conducted on February 9-12, 2009, the Chinese Lantern Festival, in Kaohsiung City. Moreover, three kinds of firework powders obtained from the same factory producing Kaohsiung Lantern Festival fireworks were burned in a combustion chamber to determine the physicochemical properties of firework aerosols. Metallic elements were analyzed with an inductively coupled plasma-atomic emission spectrometer (ICP-AES). Ionic species and carbonaceous contents in the PM samples were analyzed with an ion chromatography (IC) and an elemental analyzer (EA), respectively. Finally, the source identification and apportionment of PM were analyzed by principal component analysis (PCA), enrichment factor (EF), and receptor modeling (CMB). For inorganic gaseous pollutants, the concentration peaks of NO, NO2, O3, CO were observed during the firework periods, and the concentration peak of NO was approximately 8.8 times higher than those during the non-firework periods. This study further revealed that, even at nighttime, ambient O3 could be reduced dramatically during the firework periods, whenas NO2 concentration increased concurrently, due to titration effects resulting from the prompt reaction of NO with O3 to form NO2 and O2. For organic gaseous pollutants, the concentration peak of toluene during the firework periods was approximately 2.2-4.1 times higher than those during the non-firework periods. Several metallic elements of PM during the firework display periods were obviously higher than those during the non-firework periods. On February 10, the concentrations of Mg, K, Pb, and Sr in PM2.5 were 10 times higher than those during the non-firework periods. Besides, the Cl-/Na+ ratio was slightly smaller than 1 in Kaohsiung Harbor, but it was approximately 3 during the firework display periods since Cl- came form chlorine content in firework aerosols at this time. Moreover, OC/EC ratio increased up to 2.8. In addition to the analysis of gaseous pollutants and PM during the Chinese Lantern Festival in Kaohsiung City, this study burned firework powders in a self-designed combustion chamber to measure the physicochemical properties of firework aerosols. In the results, K, Mg, Cl-, OC were major contents (<10%) in the aerosols produced from the burning firework powders. Moreover, Cl-/Na+ and OC/EC ratio were 15.0~23.4 and 2.9~3.2, respectively. Consequently, Cl-/Na+ and OC/EC ratio can be used as two important indicators of firework displays. Results obtained from PCA and CMB receptor modeling showed that the major sources of aerosols during the firework display periods were firework displays, motor/diesel vehicle exhanst, soil dusts, and marine aerosols. Besides, the firework displays on February 10 contributed approximately 25.2% and 16.6% of PM10 at two sampling sites, respectively.

In recent years, the rapid development of economy and industry in Xiamen Bay causes serious environmental problems, particularly poor air quality and visibility impairment. There are no large-scale industrial emission sources in Kinmen Island, however, its ambient air quality is always the poorest in Taiwan. Moreover, ambient air quality monitoring data showed that PM10 concentrations varied in daytime and at nighttime. Consequently, this study tired to ascertain the potential causes for this phenomenon. This study selected ten particulate matter (PM) sampling sites at Xiamen Bay, including five sites at Kinmen Island and five sites at metro Xiamen. Particulate matter sampling was conducted in daytime (8:00-17:00) and at nighttime (17:00-8:00), which included regular and intensive sampling. Regular sampling was conducted to collect PM10 with high-volume samplers three times a month from April 2009 to April 2010, while intensive sampling was conducted to collect fine (PM2.5) and coarse (PM2.5-10) particles with dichotomous samplers and particle size distribution with a MOUDI at site B2 for consecutive 5 days in the spring and winter of 2009~2010. After sampling, the physicochemical properties of PM, including mass concentrations, particle size distribution, water- soluble ionic species, metallic elements, and carbonaceous contents were further analyzed. The level of atmospheric PM is affected by meteorological condition, thus PM10 concentrations in winter and fall was much higher than those in spring and summer. Results from backward trajectories showed that the concentrations of PM10 blown from the north were generally higher than those from the south. Furthermore, t-test analysis indicated that PM10 concentrations in daytime and at nighttime at site B3 were significantly different (p-value<0.05). During the intensive sampling periods, PM10 concentrations were mainly affected by coarse particles compared to fine particles. The highest concentration for fine and coarse particle modes occurred at the size ranges of 0.32~0.56 £gm and 3.2~5.6 £gm, respectively. The most abundant water-soluble ionic species of PM10 were secondary inorganic aerosols (SO42-, NO3-, and NH4+) which accounted for 85% of total ions. The daytime and nighttime PM10 concentration ratios (D/N) for Mg, K, Ca, Cr, Mn, Fe, Zn, Al, Cu, As, and V were in the same order of magnitude, however, the D/N ratios of Cd, Pb, Ni, and Ti in spring and summer varied higher than an order of magnitude, indicating that the emission sources of PM were different in daytime and at nighttime. Correlation analysis of OC and EC showed that OC and EC at nighttime had a higher correlation than those in daytime, while OC and EC had a higher correlation in Kinmen Island than those in metro Xiamen, indicating carbonaceous sources must be different in summer and winter at Xiamen Bay. Enrichment factor analysis revealed that ceramic industry, stone processing, and cement industry had higher correlation with PM10 concentration than utility power plants. Crustal dusts consisted of road dusts, farmland dusts, and constructive dusts, while biomass burning was not a negligible sources. Results obtained from PCA and CMB receptor modeling showed that major sources of PM in Xiamen Bay were secondary inorganic aerosols, fuel and biomass burning, marine aerosols, vehicular exhansts, and soil dusts. Besides, stone processing, cement industry, ceramic industry, and utility power plants had the highest contribution in winter. Their contributions in daytime and at nighttime were 38% and 45%, respectively.

Chemical composition of particles and rain water at three sites in Turkey were extensively compared to determine if there is a relationship between aerosol and rain composition. If such relationship exists, it can allow one to construct rain water composition using aerosol data. This is important because, rain composition data is scarce as sampling and analysis of very low concentrations of elements and ions in rain water is more difficult compared to sampling and analysis of atmospheric aerosol. Results showed that aerosol composition can be closely reflected in composition of rain water if below cloud processes dominate over the incloud processes. This is clearly observed for crustal elements in all stations and for most of the elements in urban Ankara station. However, in rural stations there were differences in rain and aerosol that is attributed to significant contribution from in cloud processes. Seasonal patterns and enrichment factors observed in aerosol composition showed general agreement with corresponding temporal variations observed in rain water concentrations of elements, but short term variations became visible only if data is averaged over a long period of time. These observations suggest that certain features of rain water composition can be constructed from if concentration data is available for aerosols. However it should be noted that there are also significant differences between stations and between elements or element groups, indicating that composition of rain water constructed from aerosol data can only be a crude one. Similarities between rain and aerosol compositions is more pronounced in urban Ankara station compared to rural stations used in this study. Factor analysis performed to aerosol and rain water data sets showed that source types affecting chemical composition of rain and particles are generally the same, bur contribution of each source type to rain and aerosol composition shows differences. Similarly, the source regions, defined by potential source contribution function, affecting aerosol and rain compositions are not identical. In Antalya station Source regions affecting chemical composition of rain water are more local compared to source regions affecting composition of aerosol. Same difference is not observed in Amasra station. Scavenging ratios is found to be a suitable tool to construct rain water composition using aerosol data. Scavenging ratios calculated using paired daily data are more variable both between stations and within a station. Long-term averaged data was found to be more reliable for calculating SRs of elements and ions at all stations.

Atmospheric haze, which builds up over South Africa including our study areas, Cape Town and the Mpumalanga Highveld under calm weather conditions, causes public concern. The scope of this study was to determine the concentration and composition of atmospheric aerosol at Khayelitsha (an urban site in the Western Cape) and Ferrobank (an industrial site in Witbank, Mpumalanga). Particulate matter was collected in Khayelitsha from 18 May 2007 to 20 July 2007 (i.e. 20 samples) using a Partisol-plus sampler and a Tapered Element Oscillating Microbalance (TEOM) sampler. Sampling took place at Ferrobank from 07 February 2008 to 11 March 2008 (6 samples) using a Partisol-plus sampler and an E-sampler. The gravimetric mass of each exposed sample was determined from pre- and post-sampling weighing. The elemental composition of the particulate matter was determined for 16 elements at Khayelitsha using Proton Induced X-ray Emission (PIXE). The concentration of the elements Al, Si, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, As, Br, Sn, and Pb was determined by analysing the PIXE spectra obtained. In similar manner, the elemental composition of the particulate matter was determined for 15 elements at Ferrobank (Al, Si, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, As, Br and Pb). The average aerosol mass concentrations for different days at the Khayelitsha site were found to vary between 8.5 μg/m3 and 124.38 μg/m3. At the Khayelitsha site on three occasions during the sampling campaign the average aerosol mass concentrations exceeded the current South African air quality standard of 75 μg/m3 over 24 h. At the Ferrobank site, there are no single days that exceeded the limit of the South African air quality standard during the sampling campaign. Enrichment factors for each element of the particles sampled with an aerodynamic diameter of less than 10 μm (PM10) samples have been calculated in order to identify their possible sources. The analysis yielded five potential sources of PM10 : soil dust, sea salt, gasoline emissions, domestic wood and coal combustion. Interestingly, enrichment factor values for the Khayelitsha samples show that sea salt constitutes a major source of emissions, while Ferrobank samples, the source apportionment by unique ratios (SPUR) indicate soil dust and coal emission are the major sources of pollution. The source apportionment at Khayelitsha shows that sea salt and biomass burning are major source of air pollution.

The environmental impact caused by oil, sewage, industrial, mining, leaching of soil and urban surfaces in the Brazilian coast has generated effluents mixed, with the metal trace a specific problem because they are deposited in marine sediments and present toxicity at the same time, persistence and bioaccumulation. Sediments act as operating compartment corded an essential role in the redistribution of marine biota, because that guard the historical record of contamination of water body. Oil exploration extends to offshore environment, occupying a prominent position in the energy matrix, responsible for most of the national supply. The oil and gas activities may include a significant source of pollution of the planet. The aim of this study was to observe the sediment profiles of the continental shelf off Sergipe and Alagoas southern state, checking for a variation of the concentration of trace metals according to depth. Three cores (PCM-9 (A), PCM-9 (B), Est.2 (A)) were performed to obtain a vertical profile of sediment samples obtained at various depths. In this study, drew up the metals Co, Cr, Fe, Li, Mn, Ni, Pb, Zn, Al and Cu total and partial, were determined by atomic absorption spectrometric (AAS). In the extraction part, the result of the recovery was above 90%, ranging from 92% to 111.1%. In the extraction result of the total recovery ranged from 77.6 to 99%. These values were obtained in the studied parameters, indicating good accuracy of the methodology. The values of RSD are below 10%, expressing the accuracy of methodology. Showed that the concentration distribution of trace metals in sediment profiles vary with depth. Colors in PCM-9 (A), PCM-9 (B), increased concentrations of metals and the core Est.2 (A) decreased gradually from base to surface. The iron was approved as a geochemical normalizer better. The values of the calculated enrichment factor shown to be low, considering the low enriched, except Pb, Co, Mn and Al that have moderate values. The geochemical background values were estimated in three different procedures, which can generate unrealistic characterizations of the state of pollution. The values of trace metals are below the sediment quality guidelines, which leads to the adverse effect on aquatic biota is unlikely. / O impacto ambiental causado por óleo, esgotamento sanitário, industrial,mineração, lixiviação de solos e superfícies urbanas, na costa brasileira temgerado efluentes variados, sendo os metais traço um problema particular,pois se depositam nos sedimentos marinho e apresentam ao mesmo tempo toxicidade, persistência e bioacumulação. Os sedimentos funcionam comocompartimento operacional que exerce papel essencial na redistribuição àbiota marinha, visto que guardam registro histórico da contaminação decorpo d água. A exploração de petróleo se estende ao ambiente offshore, ocupando uma posição de destaque na matriz energética, responsável pela maior parte do suprimento nacional. As atividades petrolíferas podem consistir uma fonte poluidora significativa do planeta. O objetivo desse estudo foi observar os perfis sedimentares da plataforma continental de Sergipe e sul de estado de Alagoas, verificando se há uma variação da concentração dos metais traço de acordo com a profundidade. Três cores (PCM-9(A), PCM-9(B), Est.2(A)) foram realizadas para obter um perfil vertical do sedimento, obtendo amostras a várias profundidades. Nesse estudo, extraiu-se os metais Co, Cr, Fe, Li, Mn, Ni, Pb, Zn, Al e Cu totais e parciais e foram determinados através da espectrometria de absorção atômica. Na extração parcial, o resultado da recuperação foi acima de 90 %, variam de 92% a 111,1%. Já na extração total o resultado da recuperação variou de 77,6 a 99%. Esses valores foram obtidos nos elementos estudados, indicando boa exatidão da metodologia. Os valores do desvio padrão relativo estão abaixo de 10%, expressando a precisão da metodologia. Mostrou-se que a distribuição da concentração dos metais traço nos perfis sedimentares variam com a profundidade. Nos cores PCM- 9(A), PCM-9 (B), as concentrações dos metais aumentaram e no core Est.2 (A) diminuiu gradativamente da base até a superfície. O ferro foi aprovado como melhor normalizador geoquímico. Os valores do fator de enriquecimento calculado mostraram-se baixos, considerando-se pouco enriquecida, exceto o Pb, Co, Mn e Al que apresentam valores moderados. Os valores de background geoquímico estimado foram diferentes nos três procedimentos utilizados. Os valores dos metais traços estão abaixo dos valores guia de qualidade dos sedimentos, o que leva o efeito adverso a biota aquática ser pouco provável.

Several scientific articles were mainly reviewed from Umeå’ s university database in order to determine the distribution, degree of contamination, and the sources of 7 selected heavy metals (Cr, Pb, Cu, Zn, Cd, Hg, Ni) in surface sediments along the coasts of the Mediterranean Sea. The Enrichment factor (EF) was used as pollution indicator to evaluate the extent of metal contamination in all the investigated areas. According to Abrahim and Parker (2008) the EF is defined as the ratio of the determined metal to Al (or Fe) in the sample divided by the ratio of background metal to background Al (or Fe) ratio. According to the results of this study, EF values for Cr, Pb, Cu, Cd and Ni presented an upward trend along the west to east shoreline of the Mediterranean sea, whereas Zn and Hg EF values showed a downward trend along this region. Cr generally exhibited no enrichment in places to the west (EF&lt;1.5) whereas in the eastern side displayed moderate enrichment (EF=1.95). Pb EF values showed moderate enrichment (EF=5) along the western section of the sea, whilst in the eastern part revealed significant enrichment (5.45). Zn pollution levels were minimal (EF=1.6) in places to the west and moderate (EF=2.2) to the east. The enrichment for Cd was considered moderate in the western part of the basin and significant in the eastern section. These heavy metals distribution can be explained by the fact that different inputs (mainly due to anthropogenic activities) from the inshore environment may take place in each area of the sea. However, Cu and Ni presented the same degree of pollution (moderate) in the whole sea, presumably indicating similar Cu and Ni inputs from the terrestrial environment. However, conclusions for Hg were not possible to be drawn as the collected data were not sufficient.

En Guinée, la disponibilité des ressources en eau est soumise à de graves problèmes de gestion avec des conséquences importantes pour les populations, notamment à Kankan où la plupart des puits tarissent pendant la saison sèche, et où la fourniture régulière de l’eau à partir de la rivière Milo n'est pas assurée dans tous les quartiers de la ville. Le Milo et son bassin versant représente donc un enjeu important pour les habitants de cette ville. Le Milo (480 km de long) qui draine un bassin versant 13 810 km2 est le plus important des affluents rive droite du Niger. Pour évaluer l’impact du bassin versant du Milo et de la ville de Kankan sur la qualité des eaux et des sédiments de ce cours d’eau, 30 échantillons de sédiments de fond ont été prélevés au cours d’une première campagne (juin-juillet 2013) sur l’ensemble des cours d’eau du bassin versant, tandis que durant une deuxième campagne (avril 2014-mai 2015), un suivi régulier a été mis en place sur le Milo en amont et en aval de Kankan. Au cours de cette dernière, 232 échantillons d’eau du Milo (dont 116 utilisés pour l’isotopie), et 26 échantillons de sédiments de fond ont été prélevés sur les stations de Bordo (amont de Kankan) et de Karifamoriah (aval de Kankan). Les concentrations en éléments majeurs et traces, terres rares, COP, COD, pH, alcalinité, l’azote organique, les isotopes de l’oxygène et de l’hydrogène, ainsi que la micro-granulométrie des sédiments ont été mesurés. Les résultats obtenus durant le cycle hydrologique 2014-2015 ont permis d’estimer le flux de matières exportées en solution par le Milo à Kankan à 47 863 t.an-1 et le flux de matières particulaires à 76 759 t.an-1. 92% de ce tonnage est exporté durant la période des hautes eaux. Ces flux permettent d’estimer des vitesses moyennes d’érosion physique (8 t.km-2.an-1) et d’altération chimique (5 t.km-2.an-1) du bassin relativement faibles. Le flux spécifique de CO2 consommé par l’altération chimique est lui aussi relativement faible (76.103 mole.km-2.an-1), mais il reste dans la moyenne des flux de CO2 mesurés sur les bassins couverts de sols latéritiques. Le degré de contamination des sédiments et sa variation spatio-temporelle ont été évalués grâce au calcul du facteur d’enrichissement (FE), en normalisant les concentrations en éléments traces par rapport à Al, Sc et Ti et en prenant le PAAS et l’UCC comme matériaux de référence. La quasi-totalité des éléments traces proviennent essentiellement des processus d’altération et sont d’origine naturelle. Toutefois, un enrichissement modéré à significatif (5 < FE < 20) a été mis en évidence pour Zr et Hf (enrichissements naturels) et As et Sb (impacts anthropiques). Finalement, l’apport anthropique en éléments traces, quand il existe, reste modéré. Les profils de concentrations en terres rares ont permis de montrer que la signature géochimique des sédiments de fond du Milo est homogène sur l’ensemble du bassin et caractéristique des sols latéritiques, non perturbée par la ville de Kankan et elle est proche des signatures du PAAS et de l’UCC. Pour l’ensemble des éléments traces et des terres rares la contribution anthropique reste faible et les fractions disponibles (phases labiles) sur les sédiments (extraction à l’EDTA) sont également faibles, confirmant ainsi que l’essentiel de ces éléments rentrent principalement dans la composition des phases résiduelles. / In Guinea, the availability of water resources is subjected to serious problems of management with important consequences for the populations, particularly in Kankan city where most of the wells dry up during the dry season and where the water supply from the Milo river is not assured for all the districts. Then the Milo river and its watershed represent an important issue for the inhabitants of Kankan. The Milo river (480 km in length) which drains an area of 13 810 km2 is the most important right-bank tributary of the Niger river. To evaluate the impact of the Milo watershed and of the Kankan city on the water and sediments of this river, 30 samples of bottom sediments have been collected during a first campaign (June-July 2013) on the main course from upstream to downstream and on the main tributaries, whereas during a second campaign (April 2014-May 2015) a regular monitoring was set up on the Milo river, upstream and downstream Kankan city. During this campaign, 232 river water samples (of which 116 for isotopic analyses) and 26 bottom sediment samples have been collected at Bordo (upstream) and Karifamoriah (downstream) stations. The concentrations of major and trace elements, rare earth elements, POC and PON, DOC, pH, alkalinity, the isotopic composition of O, H and the micro-granulometry of sediments have been measured. The results obtained during the hydrological cycle 2014-2015 allowed to estimate the fluxes of dissolved (47 863 t.y-1) and particulate (76 759 t.y-1) matters exported by the Milo river at Kankan. 92% of these fluxes are exported during the high flow period. These fluxes allowed us to estimate very low average rates of physical erosion (8 t.km-2.y-1) and chemical weathering (5 t.km-2.y-1) of the Milo catchment. The specific flux of CO2 consumed by chemical weathering (76.103 mole.km-2.y-1) is relatively low but within the range of CO2 fluxes measured in catchments draining lateritic soils. The degree of sediment contamination and its spatio-temporal variation have been assessed using the enrichment factor (EF), by normalizing the trace element concentrations with Al, Sc and Ti and by taking PAAS and UCC as the reference materials. Almost all the trace elements mainly originate from weathering processes and are of natural origin. Nevertheless, moderate to significant enrichments (5 < EF < 20) have been calculated for Zr and Hf (natural enrichments) and As and Sb (anthropogenic impacts). Finally, the anthropogenic contribution of trace elements, when it exists, remains moderate. The rare earth concentration patterns allowed to show the geochemical signature of river bottom sediments is homogeneous within the Milo catchment and characteristic of lateritic soils, non- perturbed by the city of Kankan and close to the PAAS and UCC patterns. For most of the trace and rare earth elements, the anthropogenic contribution remains low and the available fractions (labile phases) in the sediment (EDTA extraction) are also low, confirming that the main part of these elements are mainly in the residual phases.

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils and Digitaria eriantha in the vicinity of three South African coal-fired power plants, Matla, Lethabo and Rooiwal were determined by gas chromatography–mass spectrometry. An ultrasonic assisted dispersive liquid-liquid microextraction (UA-DLLME) method was developed for the extraction of polycyclic aromatic hydrocarbon in soil, followed by determination using gas chromatography mass spectrometry. The study showed that an extraction protocol based on acetonitrile as dispersive solvent and C2H2Cl2 as extracting solvent, gave extraction efficiencies comparable to conventional soxhlet extraction for soil samples. The extraction time using ultrasonication and the volume of the extraction solvent was also investigated. Using a certified reference material soil (CRM), the extraction efficiency of UA-DLLME ranged from 64 to 86% in comparison with the Soxhlet result of 73 to 95%. In comparison with the real sample, the CRM result did not show a significant difference at 95% C.I. The UA-DLLME proved to be a convenient, rapid, cost-effective and greener sample preparation approach for the determination of PAHs in soil samples. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/ Phen + Anth) were used to provide a reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g−1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g−1 for a significantly contaminated site. Calculated values of the Phen/Phen + Anth ratio were 0.48±0.08, 0.44±0.05, and 0.38+0.04 for Matla, Lethabo and Rooiwal, respectively. The flouranthene/fluoranthene + pyrene (Flan/ Flan + Pyr) levels were found to be 0.49±0.03 for Matla, 0.44±0.05 for Lethabo, and 0.53±0.08 for Rooiwal. Such values indicate a xx pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25, indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can, therefore, be concluded that the soils were contaminated with PAHs originating from coal-fired power stations. Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr and Zn) were analysed in soil and the Digitaria eriantha plant around three coal power plants (Matla, Lethabo and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05 ± 0.02 to 1835.70 ± 70 μg g-1, 0.08 ± 0.05 to 1743.90 ± 29 μg g-1 and 0.07 ± 0.04 to 1735.20 ± 91 μg g-1 at Matla, Lethabo and Rooiwal respectively. The total metal concentration in the plant (Digitaria eriantha) ranged from 0.005 ± 0.003 to 534.87 ± 43 μg g-1 at Matla, 0.002 ± 0.001 to 400.49 ± 269 μg g-1 at Lethabo and 0.002 ± 0.001 to 426.91 ± 201 μg g-1 at Rooiwal. The accumulation factor (A) of less than 1 (i.e. 0.003 to 0.37) at power plants indicates a low transfer of metal from soil to plant (excluder). The enrichment factor values obtained (2.4 – 5) indicate that the soils are moderately enriched, with the exception of Pb that had significant enrichment of 20. The Geo-accumulation Index values of metals indicate that the soils are moderately polluted (0.005 – 0.65), except for Pb that showed moderate to strong pollution (1.74 – 2.53). / Chemistry / D. Phil. (Chemistry)

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils and Digitaria eriantha in the vicinity of three South African coal-fired power plants, Matla, Lethabo and Rooiwal were determined by gas chromatography–mass spectrometry. An ultrasonic assisted dispersive liquid-liquid microextraction (UA-DLLME) method was developed for the extraction of polycyclic aromatic hydrocarbon in soil, followed by determination using gas chromatography mass spectrometry. The study showed that an extraction protocol based on acetonitrile as dispersive solvent and C2H2Cl2 as extracting solvent, gave extraction efficiencies comparable to conventional soxhlet extraction for soil samples. The extraction time using ultrasonication and the volume of the extraction solvent was also investigated. Using a certified reference material soil (CRM), the extraction efficiency of UA-DLLME ranged from 64 to 86% in comparison with the Soxhlet result of 73 to 95%. In comparison with the real sample, the CRM result did not show a significant difference at 95% C.I. The UA-DLLME proved to be a convenient, rapid, cost-effective and greener sample preparation approach for the determination of PAHs in soil samples. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/ Phen + Anth) were used to provide a reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g−1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g−1 for a significantly contaminated site. Calculated values of the Phen/Phen + Anth ratio were 0.48±0.08, 0.44±0.05, and 0.38+0.04 for Matla, Lethabo and Rooiwal, respectively. The flouranthene/fluoranthene + pyrene (Flan/ Flan + Pyr) levels were found to be 0.49±0.03 for Matla, 0.44±0.05 for Lethabo, and 0.53±0.08 for Rooiwal. Such values indicate a xx pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25, indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can, therefore, be concluded that the soils were contaminated with PAHs originating from coal-fired power stations. Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr and Zn) were analysed in soil and the Digitaria eriantha plant around three coal power plants (Matla, Lethabo and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05 ± 0.02 to 1835.70 ± 70 μg g-1, 0.08 ± 0.05 to 1743.90 ± 29 μg g-1 and 0.07 ± 0.04 to 1735.20 ± 91 μg g-1 at Matla, Lethabo and Rooiwal respectively. The total metal concentration in the plant (Digitaria eriantha) ranged from 0.005 ± 0.003 to 534.87 ± 43 μg g-1 at Matla, 0.002 ± 0.001 to 400.49 ± 269 μg g-1 at Lethabo and 0.002 ± 0.001 to 426.91 ± 201 μg g-1 at Rooiwal. The accumulation factor (A) of less than 1 (i.e. 0.003 to 0.37) at power plants indicates a low transfer of metal from soil to plant (excluder). The enrichment factor values obtained (2.4 – 5) indicate that the soils are moderately enriched, with the exception of Pb that had significant enrichment of 20. The Geo-accumulation Index values of metals indicate that the soils are moderately polluted (0.005 – 0.65), except for Pb that showed moderate to strong pollution (1.74 – 2.53). / Chemistry / D. Phil. (Chemistry)