Chemical analysis and reactivity of biomass pyrolysis products. Application to the development of carbon-neutral biofuels and chemicals

In this dissertation the pyrolytic conversion of biomass into chemicals and fuels was investigated from the analytical point of view. The study was focused on the liquid (bio-oil) and solid (char) fractions obtainable from biomass pyrolysis. The drawbacks of Py-GC-MS described so far were partially solved by coupling different analytical configurations (Py-GC-MS, Py-GC-MIP-AED and off-line Py-SPE and Py-SPME-GC-MS with derivatization procedures). The application of different techniques allowed a satisfactory comparative analysis of pyrolysis products of different biomass and a high throughput screening on effect of 33 catalysts on biomass pyrolysis. As the results of the screening showed, the most interesting catalysts were those containing copper (able to reduce the high molecular weight fraction of bio-oil without large yield decrease) and H-ZSM-5 (able to entirely convert the bio-oil into “gasoline like” aromatic products). In order to establish the noxious compounds content of the liquid product, a clean-up step was included in the Py-SPE procedure. This allowed to investigate pollutants (PAHs) generation from pyrolysis and catalytic pyrolysis of biomass. In fact, bio-oil from non-catalytic pyrolysis of biomass showed a moderate PAHs content, while the use of H-ZSM-5 catalyst for bio-oil up-grading determined an astonishing high production of PAHs (if compared to what observed in alkanes cracking), indicating an important concern in the substitution fossil fuel with bio-oil derived from biomass. Moreover, the analytical procedures developed in this thesis were directly applied for the detailed study of the most useful process scheme and up-grading route to chemical intermediates (anhydrosugars), transportation fuels or commodity chemicals (aromatic hydrocarbons). In the applied study, poplar and microalgae biomass were investigated and overall GHGs balance of pyrolysis of agricultural residues in Ravenna province was performed. A special attention was put on the comparison of the effect of bio-char different use (fuel or as soil conditioner) on the soil health and GHGs emissions.

Automatisierte Flüssigchromatographie mit Säulenschaltung und Ultraviolettspektroskopie oder Massenspektrometrie für therapeutisches Drug Monitoring von Antipsychotika und Antidepressiva

Therapeutisches Drug Monitoring (TDM) wird zur individuellen Dosiseinstellung genutzt, um die Effizienz der Medikamentenwirkung zu steigern und das Auftreten von Nebenwirkungen zu senken. Für das TDM von Antipsychotika und Antidepressiva besteht allerdings das Problem, dass es mehr als 50 Medikamente gibt. Ein TDM-Labor muss dementsprechend über 50 verschiedene Wirkstoffe und zusätzlich aktive Metaboliten messen. Mit der Flüssigchromatographie (LC oder HPLC) ist die Analyse vieler unterschiedlicher Medikamente möglich. LC mit Säulenschaltung erlaubt eine Automatisierung. Dabei wird Blutserum oder -plasma mit oder ohne vorherige Proteinfällung auf eine Vorsäule aufgetragen. Nach Auswaschen von störenden Matrixbestandteilen werden die Medikamente auf einer nachgeschalteten analytischen Säule getrennt und über Ultraviolettspektroskopie (UV) oder Massenspektrometrie (MS) detektiert. Ziel dieser Arbeit war es, LC-Methoden zu entwickeln, die die Messung möglichst vieler Antipsychotika und Antidepressiva erlaubt und die für die TDM-Routine geeignet ist. Eine mit C8-modifiziertem Kieselgel gefüllte Säule (20 µm 10x4.0 mm I.D.) erwies sich in Vorexperimenten als optimal geeignet bezüglich Extraktionsverhalten, Regenerierbarkeit und Stabilität. Mit einer ersten HPLC-UV-Methode mit Säulenschaltung konnten 20 verschiedene Psychopharmaka einschließlich ihrer Metabolite, also insgesamt 30 verschiedene Substanzen quantitativ erfasst werden. Die Analysenzeit betrug 30 Minuten. Die Vorsäule erlaubte 150 Injektionen, die analytische Säule konnte mit mehr als 300 Plasmainjektionen belastet werden. Abhängig vom Analyten, musste allerdings das Injektionsvolumen, die Flussrate oder die Detektionswellenlänge verändert werden. Die Methode war daher für eine Routineanwendung nur eingeschränkt geeignet. Mit einer zweiten HPLC-UV-Methode konnten 43 verschiedene Antipsychotika und Antidepressiva inklusive Metaboliten nachgewiesen werden. Nach Vorreinigung über C8-Material (10 µm, 10x4 mm I.D.) erfolgte die Trennung auf Hypersil ODS (5 µm Partikelgröße) in der analytischen Säule (250x4.6 mm I.D.) mit 37.5% Acetonitril im analytischen Eluenten. Die optimale Flussrate war 1.5 ml/min und die Detektionswellenlänge 254 nm. In einer Einzelprobe, konnten mit dieser Methode 7 bis 8 unterschiedliche Substanzen gemessen werden. Für die Antipsychotika Clozapin, Olanzapin, Perazin, Quetiapin und Ziprasidon wurde die Methode validiert. Der Variationskoeffizient (VK%) für die Impräzision lag zwischen 0.2 und 6.1%. Im erforderlichen Messbereich war die Methode linear (Korrelationskoeffizienten, R2 zwischen 0.9765 und 0.9816). Die absolute und analytische Wiederfindung lagen zwischen 98 und 118 %. Die für das TDM erforderlichen unteren Nachweisgrenzen wurden erreicht. Für Olanzapin betrug sie 5 ng/ml. Die Methode wurde an Patienten für das TDM getestet. Sie erwies sich für das TDM als sehr gut geeignet. Nach retrospektiver Auswertung von Patientendaten konnte erstmalig ein möglicher therapeutischer Bereich für Quetiapin (40-170 ng/ml) und Ziprasidon (40-130 ng/ml) formuliert werden. Mit einem Massenspektrometer als Detektor war die Messung von acht Neuroleptika und ihren Metaboliten möglich. 12 Substanzen konnten in einem Lauf bestimmt werden: Amisulprid, Clozapin, N-Desmethylclozapin, Clozapin-N-oxid, Haloperidol, Risperidon, 9-Hydroxyrisperidon, Olanzapin, Perazin, N-Desmethylperazin, Quetiapin und Ziprasidon. Nach Vorreinigung mit C8-Material (20 µm 10x4.0 mm I.D.) erfolgte die Trennung auf Synergi MAX-RP C12 (4 µm 150 x 4.6 mm). Die Validierung der HPLC-MS-Methode belegten einen linearen Zusammenhang zwischen Konzentration und Detektorsignal (R2= 0,9974 bis 0.9999). Die Impräzision lag zwischen 0.84 bis 9.78%. Die für das TDM erforderlichen unteren Nachweisgrenzen wurden erreicht. Es gab keine Hinweise auf das Auftreten von Ion Suppression durch Matrixbestandteile. Die absolute und analytische Wiederfindung lag zwischen 89 und 107 %. Es zeigte sich, dass die HPLC-MS-Methode ohne Modifikation erweitert werden kann und anscheinend mehr als 30 verschiedene Psychopharmaka erfasst werden können. Mit den entwickelten flüssigchromatographischen Methoden stehen neue Verfahren für das TDM von Antipsychotika und Antidepressiva zur Verfügung, die es erlauben, mit einer Methode verschiedene Psychopharmaka und ihre aktiven Metabolite zu messen. Damit kann die Behandlung psychiatrischer Patienten insbesondere mit Antipsychotika verbessert werden.

Valutazione ambientale di tecnologie di bonifica per acquiferi contaminati attraverso la metodologia LCA

La bonifica di acquiferi contaminati è una pratica che oggi dispone di diverse soluzioni a livello tecnologico, caratterizzate tuttavia da costi (ambientali ed economici) e problematiche tecniche di entità tale da rendere in alcuni casi poco conveniente la realizzazione dell’intervento stesso. Per questo motivo sempre maggiore interesse viene rivolto nell’ambito della ricerca alle tecnologie di bioremediation, ovvero sistemi in cui la degradazione degli inquinanti avviene ad opera di microorganismi e batteri opportunamente selezionati e coltivati. L’impiego di queste tecniche consente un minor utilizzo di risorse ed apparati tecnologici per il raggiungimento degli obiettivi di bonifica rispetto ai sistemi tradizionali. Il lavoro di ricerca presentato in questa tesi ha l’obiettivo di fornire, tramite l’utilizzo della metodologia LCA, una valutazione della performance ambientale di una tecnologia di bonifica innovativa (BEARD) e due tecnologie largamente usate nel settore, una di tipo passivo (Permeable Reactive Barrier) ed una di tipo attivo (Pump and Treat con Carboni Attivi).

Ten Years after the Chernobyl Accident: Long-Term Immunological Consequences; Prognosis of Autoimmune Disorders

The Chernobyl tragedy was the biggest accident since the beginning of the nuclear power industry. The aim of this study was to determine the role of immunological mechanisms in the development of autoimmune disorders (thyroiditis and cataract) and cancers among those workers who participated in clean-up operations in 1986. Blood samples from 165 clean-up workers aged 30-65 from Minsk and Kiev who underwent prophylactic medical examinations and from 80 healthy donors were investigated for the presence of autoimmune reactions and the appearance of onco-foetal antigens. The sera of clean-up workers were found to include the thyroid gland antigen, auto-antibodies to thyroid gland and eye antigens, and immune complexes which are normally absent or found in much lower quantities. The appearance of the clinically unmanifested thyroid gland antigen made it possible to generate a concept describing the mechanism for induction and long-term maintenance of auto-antibody production in an organism after irradiation. Lymphocytes from clean-up workers showed normally absent onco-foetal antigens (PSG and CEA). The data obtained indicate that clean-up workers represent a high risk group for autoimmune and cancer diseases. Immunological findings reveal the long-lasting effects of low doses of irradiation and may be used in prognosis and monitoring of human health.

Comparison of Various Methods of Estrus Detection in Synchronized Virgin Beef Heifers

Methods of heat detection were compared in the Mid- Crest Area Cattle Evaluation Program (MACEP) heifer development program in the 1998-breeding season. A total of 189 heifers from thirteen consignors entered the program on November 10, 1997. These heifers were condition scored, hip height measured, weighed, disposition scored, booster vaccinated, and treated for parasites at the time of arrival. Determination of the heifer’s mature weight was made and a target of 65% of their mature weight at breeding was established. The ration was designed to meet this goal. The heifers were kept in a dry lot until all heifers were AI bred once. The heifers were periodically weighed and condition scored to monitor their gains and the ration was adjusted as needed. The estrus synchronization program consisted of an oral progesterone analog for 14 days; 17 days after completion of the progesterone analog treatment a single injection of prostaglandin was given and the heifers were then estrus detected. Two concurrent methods of estrus detection were utilized: 1) Ovatec â electronic breeding probe (probe), 2) HeatWatchâ estrus detection system (HW), and 3) a combination of probe and HW. Probe readings were obtained each 12 hours and the heifers were continuously monitored for estrus activity using the HW system. The probe was used as the primary estrus detection method and the HW system was used as a back-up system. Those heifers that did not demonstrate any estrus signs prior to 96 hours post prostaglandin treatment were mass inseminated at 96 hours. Post AI breeding, 151 of the heifers were placed on pasture and ran with clean-up bulls for 60 days. The remaining heifers left the program after the AI breeding was completed. Pregnancy to the AI breeding was determined by ultrasound on June 29, 1998. Results from using both probe and HW were 60% pregnant by AI, probe alone was 32% pregnant by AI, and HW alone was 27% pregnant by AI. The result of mass insemination was 20% pregnant by AI.

Water–montmorillonite systems: Neutron scattering and tracer throughdiffusion studies

Designs for deep geological respositories of nuclear waste include bentonite as a hydraulic and chemisorption buffer material to protect the biosphere from leakage of radionuclides. Bentonite is chosen because it is a cheap, naturally occurring material with the required properties. It consists essentially of montmorillonite, a swelling clay mineral. Upon contact with groundwater such clays can seal the repository by incorporating water in the interlayers of their crystalline structure. The intercalated water exhibits significantly different properties to bulk water in the surrounding interparticle pores, such as lower diffusion coefficients (González Sánchez et. al. 2008). This doctoral thesis presents water distribution and diffusion behavior on various time and space scales in montmorillonite. Experimental results are presented for Na- and Cs-montmorillonite samples with a range of bulk dry densities (0.8 to 1.7 g/cm3). The experimental methods employed were neutron scattering (backscattering, diffraction, time-of-flight), adsorption measurements (water, nitrogen) and tracer-through diffusion. For the tracer experiments the samples were fully saturated via the liquid phase under volume-constrained conditions. In contrast, for the neutron scattering experiments, the samples were hydrated via the vapor phase and subsequently compacted, leaving a significant fraction of interparticle pores unfilled with water. Owing to these differences in saturation, the water contents of the samples for neutron scattering were characterized by gravimetry whereas those for the tracer experiments were obtained from the bulk dry density. The amount of surface water in interlayer pores could be successfully discriminated from the amount of bulk-like water in interparticle pores in Na- and Csmontmorillonite using neutron spectroscopy. For the first time in the literature, the distribution of water between these two pore environments was deciphered as a function of gravimetric water content. The amount was compared to a geometrical estimation of the amount of interlayer and interparticle water determined by neutron diffraction and adsorption measurements. The relative abundances of the 1 to 4 molecular water layers in the interlayer were determined from the area ratios of the (001)-diffraction peaks. Depending on the characterization method, different fractions of surface water and interlayer water were obtained. Only surface and interlayer water exists in amontmorillonite with water contents up to 0.18 g/g according to spectroscopic measurements and up to 0.32 g/g according to geometrical estimations, respectively. At higher water contents, bulk-like and interparticle water also exists. The amounts increase monotonically, but not linearly, from zero to 0.33 g/g for bulk-like water and to 0.43 g/g for interparticle water. It was found that water most likely redistributes between the surface and interlayer sites during the spectroscopic measurements and therefore the reported fraction is relevant only below about -10 ºC (Anderson, 1967). The redistribution effect can explain the discrepancy in fractions between the methods. In a novel approach the fractions of water in different pore environments were treated as a fixed parameter to derive local diffusion coefficients for water from quasielastic neutron scattering data, in particular for samples with high water contents. Local diffusion coefficients were obtained for the 1 to 4 molecular water layers in the interlayer of 0.5·10–9, 0.9·10–9, 1.5·10–9 and 1.4·10–9 m²/s, respectively, taking account of the different water fractions (molecular water layer, bulk-like water). The diffusive transport of 22Na and HTO through Na-montmorillonite was measured on the laboratory experimental scale (i.e. cm, days) by tracer through-diffusion experiments. We confirmed that diffusion of HTO is independent of the ionic strength of the external solution in contact with the clay sample but dependent on the bulk dry density. In contrast, the diffusion of 22Na was found to depend on both the ionic strength of the pore solution and on the bulk dry density. The ratio of the pore and surface diffusion could be experimentally determined for 22Na from the dependence of the diffusion coefficient on the ionic strength. Activation energies were derived from the temperaturedependent diffusion coefficients via the Arrhenius relation. In samples with high bulk dry density the activation energies are slightly higher than those of bulk water whereas in low density samples they are lower. The activation energies as a function of ionic strengths of the pore solutions are similar for 22Na and HTO. The facts that (i) the slope of the logarithmic effective diffusion coefficients as a function of the logarithmic ionic strength is less than unity for low bulk dry densities and (ii) two water populations can be observed for high gravimetric water contents (low bulk dry densities) support the interlayer and interparticle porosity model proposed by Glaus et al. (2007), Bourg et al. (2006, 2007) and Gimmi and Kosakowski (2011).

Inverse fusion PCR cloning.

Inverse fusion PCR cloning (IFPC) is an easy, PCR based three-step cloning method that allows the seamless and directional insertion of PCR products into virtually all plasmids, this with a free choice of the insertion site. The PCR-derived inserts contain a vector-complementary 5'-end that allows a fusion with the vector by an overlap extension PCR, and the resulting amplified insert-vector fusions are then circularized by ligation prior transformation. A minimal amount of starting material is needed and experimental steps are reduced. Untreated circular plasmid, or alternatively bacteria containing the plasmid, can be used as templates for the insertion, and clean-up of the insert fragment is not urgently required. The whole cloning procedure can be performed within a minimal hands-on time and results in the generation of hundreds to ten-thousands of positive colonies, with a minimal background.

A Model Study of the Circulation in the Pearl River Estuary (PRE) and Its Adjacent Coastal Waters: 2. Sensitivity Experiments

The Princeton Ocean Model is used to study the circulation in the Pear River Estuary (PRE) and the adjacent coastal waters in the winter and summer seasons. Wong et al. [2003] compares the simulation results with the in situ measurements collected during the Pearl River Estuary Pollution Project (PREPP). In this paper, sensitivity experiments are carried out to examine the plume and the associated frontal dynamics in response to seasonal discharges and monsoon winds. During the winter, convergence between the seaward spreading plume water and the saline coastal water sets up a salinity front that aligns from the northeast to the southwest inside the PRE. During the summer the plume water fills the PRE at the surface and spreads eastward in the coastal waters in response to the prevailing southwesterly monsoon. The overall alignment of the plume is from the northwest to the southeast. The subsurface front is similar to that in the winter and summer except that the summer front is closer to the mouth and the winter front closer to the head of the estuary. Inside the PRE, bottom flows are always toward the head of the estuary, attributed to the density gradient associated with the plume front. In contrast, bottom flows in the shelf change from offshore in winter to onshore in summer, reflecting respectively the wintertime downwelling and summertime upwelling. Wind also plays an essential role in controlling the plume at the surface. An easterly wind drives the plume westward regardless winter or summer. The eastward spreading of the plume during the summer can be attributed to the southerly component of the wind. On the other hand, the surface area of the plume is positively proportional to the amount of discharge.

SUPERFUND: AN ANALYSIS OF IMPLEMENTATION FAILURE (CERCLA, HEALTH LAW POLICY)

In December, 1980, following increasing congressional and constituent-interest in problems associated with hazardous waste, the Comprehensive Environmental Recovery, Compensation and Liability Act (CERCLA) was passed. During its development, the legislative initiative was seriously compromised which resulted in a less exhaustive approach than was formerly sought. Still, CERCLA (Superfund) which established, among other things, authority to clean up abandoned waste dumps and to respond to emergencies caused by releases of hazardous substances was welcomed by many as an important initial law critical to the cleanup of the nation's hazardous waste. Expectations raised by passage of this bill were tragically unmet. By the end of four years, only six sites had been declared by the EPA as cleaned. Seemingly, even those determinations were liberal; of the six sites, two were identified subsequently as requiring further cleanup.^ This analysis is focused upon the implementation failure of the Superfund. In light of that focus, discussion encompasses development of linkages between flaws in the legislative language and foreclosure of chances for implementation success. Specification of such linkages is achieved through examination of the legislative initiative, identification of its flaws and characterization of attendant deficits in implementation ability. Subsequent analysis is addressed to how such legislative frailities might have been avoided and to attendant regulatory weaknesses which have contributed to implementation failure. Each of these analyses are accomplished through application of an expanded approach to the backward mapping analytic technique as presented by Elmore. Results and recommendations follow.^ Consideration is devoted to a variety of regulatory issues as well as to those pertinent to legislative and implementation analysis. Problems in assessing legal liability associated with hazardous waste management are presented, as is a detailed review of the legislative development of Superfund, and its initial implementation by Gorsuch's EPA. ^

An assessment of post-disaster psychological stress in hazardous waste operations and emergency response (HAZWOPER) workers

Personnel involved in natural or man-made disaster response and recovery efforts may be exposed to a wide variety of physical and mental stressors that can exhibit long-lasting and detrimental psychopathological outcomes. In a disaster situation, huge numbers of "secondary" responders can be involved in contaminant clean-up and debris removal and can be at risk of developing stress-related mental health outcomes. The Occupational Safety and Health Administration (OSHA) worker training hierarchy typically required for response workers, known as "Hazardous Waste Operations and Emergency Response" (HAZWOPER), does not address the mental health and safety concerns of workers. This study focused on the prevalence of traumatic stress experienced by secondary responders that had received or expressed interest in receiving HAZWOPER training through the National Institute of Environmental Health Sciences Worker Education and Training Program (NIEHS WETP). ^ The study involved the modification of two preexisting and validated survey tools to assess secondary responder awareness of physical, mental, and traumatic stressors on mental health and sought to determine if a need existed to include traumatic stress-related mental health education in the current HAZWOPER training regimen. The study evaluated post-traumatic stress disorder (PTSD), resiliency, mental distress, and negative effects within a secondary responder population of 176 respondents. Elevated PTSD levels were seen in the study population as compared to a general responder population (32.9% positive vs. 8%-22.5% positive). Results indicated that HAZWOPER-trained disaster responders were likely to test positive for PTSD, whereas, untrained responders with no disaster experience and responders who possessed either training or disaster experience only were likely to test PTSD negative. A majority (68.75%) of the population tested below the mean resiliency to cope score (80.4) of the average worker population. Results indicated that those who were trained only or who possessed both training and disaster work experience were more likely to have lower resiliency scores than those with no training or experience. There were direct correlations between being PTSD positive and having worked at a disaster site and experiencing mental distress and negative effects. However, HAZWOPER training status does not significantly correlate with mental distress or negative effect. ^ The survey indicated clear support (91% of respondents) for mental health education. The development of a pre- and post-deployment training module is recommended. Such training could provide responders with the necessary knowledge and skills to recognize the symptomology of PTSD, mental stressors, and physical and traumatic stressors, thus empowering them to employ protective strategies or seek professional help if needed. It is further recommended that pre-deployment mental health education be included in the current HAZWOPER 24- and 40-hour course curriculums, as well as, consideration be given towards integrating a stand-alone post-deployment mental health education training course into the current HAZWOPER hierarchy.^

Gestión de efluentes y consumo de agua en bodega

Se estudió la gestión de efluentes y el consumo de agua en una bodega productora de vinos tintos ubicada en Maipú (Mendoza, Argentina) y se propusieron alternativas para mejorar la situación actual organizando y reduciendo el consumo de agua y disminuyendo el impacto ambiental que causan los efluentes. La empresa no mide con precisión el consumo de agua, estimándolo por las veces que se llena y vacía la pileta que recoge los efluentes. Con ese dato, y en función del volumen elaborado de vino, se infirió que el gasto de agua quintuplica aproximadamente al de un establecimiento similar en Francia. Tampoco son medidas la salinidad y la toxicidad de las aguas residuales. Los cambios propuestos se basaron en: • la medición de los flujos de aguas de lavado y efluentes; • la reducción del consumo de agua adaptando materiales y maquinarias; estableciendo protocolos de limpieza y sensibilizando e instruyendo al personal; • la separación de los efluentes tóxicos; • la separación eficiente de los residuos sólidos de los líquidos; • los tratamientos oxidativos en aguas efluentes; • la reutilización parcial de las aguas tratadas en usos no bromatológicos.

Stable isotope record of planktonic foraminifera of the South Atlantic

The central problem of late Quaternary circulation in the South Atlantic is its role in transfer of heat to the North Atlantic, as this modifies amplitude, and perhaps phase, of glacialinterglacial fluctuations. Here we attempt to define the problem and establish ways to attack it. We identify several crucial elements in the dynamics of heat export: (1) warm-water pile-up (and lack thereof) in the Western equatorial Atlantic, (2) general spin-up (or spin-down) of central gyre, tied to SE trades, (3) opening and closing of Cape Valve (Agulhas retroflection), (4) deepwater E-W asymmetry. Means for reconstruction are biogeography, stable isotopes, and productivity proxies. Main results concern overall glacial-interglacial contrast (less pile-up, more spin-up, Cape Valve closed, less NADW during glacial time), dominance of precessional signal in tropics, phase shifts in precessional response. To generate working hypotheses about the dynamics of surface water circulation in the South Atlantic we employ Croll's paradigm that glacial - interglacial fluctuations are analogous to seasonal fluctuations. Our general picture for the last 300 kyrs is that, as concerns the South Atlantic, intensity of surface water (heat) transport depends on the strength of the SE trades. From various lines of evidence it appears that strenger SE trades appeared during glacials and cold substages during interglacials, analogous to conditions in southern winter (August).

Geochemistry of sediments cores in the Mediterranean Sea

We investigated five time-equivalent core sections (180-110 kyr BP) from the Balearic Sea (Menorca Rise), the easternmost Levantine Basin and southwest, south, and southeast of Crete to reconstruct spatial patterns of productivity during deposition of sapropels S5 and S6 in the Mediterranean Sea. Our indicators are Ba, total organic carbon and carbonate contents. We found no indications of Ba remobilization within the investigated core intervals, and used the accumulation rate of biogenic Ba to compute paleoproductivity. Maximum surface water productivity (up to 350 g C/m2/yr) was found during deposition of S5 (isotope stage 5e) but pronounced spatial variability is evident. Coeval sediment intervals in the Balearic Sea show very little productivity change, suggesting that chemical and biological environments in the eastern and western Mediterranean basins were decoupled in this interval. We interpret the spatial variability as the result of two different modes of nutrient delivery to the photic zone: riverderived nutrient input and shoaling of the pycnocline/nutricline to the photic zone. The productivity increase during the formation of S6 was moderate compared to S5 and had a less marked spatial variability within the study area of the eastern Mediterranean Sea. Given that S6 formed during a glacial interval, glacial boundary conditions such as high wind stress and/or cooler surface water temperatures apparently favored lateral and vertical mixing and prevented the development of the spatial gradients within the Eastern Mediterranean Sea (EMS) observed for S5. A non-sapropel sediment interval with elevated Ba content and depleted 18O/16O ratios in planktonic foraminifer calcite was detected between S6 and S5 that corresponds to the weak northern hemisphere insolation maximum at 150 kyr. At this time, productivity apparently increased up to five times over surrounding intervals, but abundant benthic fauna show that the deep water remained oxic. Following our interpretation, the interval denotes a failed sapropel, when a weaker monsoon did not force the EMS into permanent stratification. The comparison of interglacial and glacial sapropels illustrates the relevance of climatic boundary conditions in the northern catchment in determining the facies and spatial variability of sapropels within the EMS.

Planktological-chemical observation during the International Indian Ocean Expedition (IIOE) with RV "Meteor" in 1964/65

The present volume contains the planktological data collected during the expedition of the "Meteor" to the Indian Ocean in 1964/65. It was the main objective of the expedition to study the up- and downwelling conditioned along the western and eastern coasts of the Arabian Sea by the northeastern monsoon. It is from these areas that the greater part of the data here presented was obtained. A few values from the Red Sea have been added. As the title "Planktological-Chemical Data" implies, it was chiefly with the help of chemical methods that the planktological investigations, with the exception of the particle size analysis and phytoplankton counting conducted optically, were carried out. These investigations were above all devoted to a quantitative survey of particulate matter and plankton, the latter being sampled by water-bottle and net. The zooplankton hauls were taken with the Indian Ocean Standard Net according to the international guidelines laid down for the expedition. As a rule, double catches were made at every station, one sample being intended for laboratory analysis at the Indian Ocean Biological Centre in Ernakulam, South India, and the other for the Institut für Meereskunde in Kiel. In addition to determining the standing stock, the production rate of phytoplankton was measured by the 14C method. These experiments were mainly conducted during the latter half of the expedition. The planktological studies primarily covered the euphotic zone, extending into the underlying water layers up to a depth of 600 m. The investigations were above all directed towards ascertaining the quantity of organic substance, formed by primary production, in its relation to environmental conditions and determining whether or not organic substance is actively transported from the surface into the deeper layers by the periodically migration organisms of the deep scattering layers. Depending on the station time available, a few samples could now and then be taken from deeper layers. The present volume of planktological-chemical data addresses itself to all those concerned processing the extensive material collected during the International Indian Ocean Expedition. As a readily accessible work of reference, it hopes to serve as an aid in the evaluation and interpretation of the expedition results. The complementary ecological data such as temperature, salinity, and oxygen content as well as the figures obtained on abundance and distribution in depth of the nutrients essential for primary production may be found in the volume of physical-chemical data published in Series A of the "Meteor"-Forschungsergebnisse No. 2, 1966 (Dietrich et al., 1966).

Bioremediation of oil spills

Due to the increasing demand of petroleum everywhere, and the great amount of spills, accidents and disasters, there is an urgent need to find an effective, non-cost and harmless method to clean up the affected areas. There are microorganisms in nature (bacteria and fungi, mainly) that feed on hydrocarbons and transform them into others harmless chemical substances. These bacteria produce enzymes that degrade oil very effectively. This natural process can be accelerated by adding more bacteria or providing nutrients and oxygen to facilitate their growth, which is called ―bioaugmentation and biostimulation. Through this project we discover that these processes can be affected by different factors making difficult the biodegradation execution and opening a gap between the laboratory experiments and the real cases. Therefore, there is much remain to be done and a lot of study ahead to make this technique available in a great scale.