Transport of pollutants through the water and subsurface soil using simulated acid rain

The mobility of heavy metals (Zn, Cd, Pb and Ni) was studied in the laboratory acidic leaching two different soils around Ibadan with simulated acid rain. The sampling was carried out from two different sites viz: Orogun and Ilupeju respectively. For Orogun site a depth of 128cm was reached (consisting of four horizons). Different length of polyvinyl chloride (PVC) pipes were cut for different soil horizon depth as observed on the field. The PVC pipes were packed with requires masses of soil. This is then leached using simulated acid rain of different pH of 2.0, 4.0, 6.0 and 8.0 after spiking with known volume of standard solution of metals of interest. It was found that simulated acid rain enhanced the mobility of metals in solution. The pH, Cation Exchange capacity, % clay and organic matter were found to contributed majority to the mobility of metals. Generally as observed, the mobility of metal was to follow the order Zn>Ni>Pb>Cd as the soil is becoming more acidic

Electron tunneling in proteins and water

The subject of this thesis is electronic coupling in donor-bridge-acceptor systems. In Chapter 2, ET properties of cyanide-bridged dinuclear ruthenium complexes were investigated. The strong interaction between the mixed-valent ruthenium centers leads to intense metal-to-metal charge transfer bands (MMCT). Hush analysis of the MMCT absorption bands yields the electronic-coupling strength between the metal centers (H_(AB)) and the total reorganization energy (λ). Comparison of ET kinetics to calculated rates shows that classical ET models fail to account for the observed kinetics and nuclear tunneling must be considered.

In Chapter 3, ET rates were measured in four ruthenium-modified highpotential iron-sulfur proteins (HiPIP), which were modified at position His50, His81, His42 and His18, respectively. ET kinetics for the His50 and His81 mutants are a factor of 300 different, while the donor-acceptor separation is nearly identical. PATHWAY calculations corroborate these measurements and highlight the importance of structural detail of the intervening protein matrix.

In Chapter 4, the distance dependence of ET through water bridges was measured. Photoinduced ET measurements in aqueous glasses at 77 K show that water is a poor medium for ET. Luminescence decay and quantum yield data were analyzed in the context of a quenching model that accounts for the exponential distance dependence of ET, the distance distribution of donors and acceptors embedded in the glass and the excluded volumes generated by the finite sizes of the donors and acceptors.

In Chapter 5, the pH-dependent excited state dynamics of ruthenium-modified amino acids were measured. The [Ru(bpy)_(3)] ^(2+) chromophore was linked to amino acids via an amide linkage. Protonation of the amide oxygen effectively quenches the excited state. In addition. time-resolved and steady-state luminescence data reveal that nonradiative rates are very sensitive to the protonation state and the structure of the amino acid moiety.

Oxidation of Volatile Organic Compounds in Aqueous Solution and at the Air-water Interface of Aqueous Microdroplets

Isoprene (ISO),the most abundant non-methane VOC, is the major contributor to secondary organic aerosols (SOA) formation. The mechanisms involved in such transformation, however, are not fully understood. Current mechanisms, which are based on the oxidation of ISO in the gas-phase, underestimate SOA yields. The heightened awareness that ISO is only partially processed in the gas-phase has turned attention to heterogeneous processes as alternative pathways toward SOA.

During my research project, I investigated the photochemical oxidation of isoprene in bulk water. Below, I will report on the λ > 305 nm photolysis of H₂O₂ in dilute ISO solutions. This process yields C₁₀H₁₅OH species as primary products, whose formation both requires and is inhibited by O₂. Several isomers of C₁₀H₁₅OH were resolved by reverse-phase high-performance liquid chromatography and detected as MH⁺ (m/z = 153) and MH⁺-18 (m/z = 135) signals by electrospray ionization mass spectrometry. This finding is consistent with the addition of ·OH to ISO, followed by HO-ISO· reactions with ISO (in competition with O₂) leading to second generation HO(ISO)₂· radicals that terminate as C₁₀H₁₅OH via β-H abstraction by O₂.

It is not generally realized that chemistry on the surface of water cannot be deduced, extrapolated or translated to those in bulk gas and liquid phases. The water density drops a thousand-fold within a few Angstroms through the gas-liquid interfacial region and therefore hydrophobic VOCs such as ISO will likely remain in these relatively 'dry' interfacial water layers rather than proceed into bulk water. In previous experiments from our laboratory, it was found that gas-phase olefins can be protonated on the surface of pH < 4 water. This phenomenon increases the residence time of gases at the interface, an event that makes them increasingly susceptible to interaction with gaseous atmospheric oxidants such as ozone and hydroxyl radicals.

In order to test this hypothesis, I carried out experiments in which ISO(g) collides with the surface of aqueous microdroplets of various compositions. Herein I report that ISO(g) is oxidized into soluble species via Fenton chemistry on the surface of aqueous Fe(II)Cl₂ solutions simultaneously exposed to H₂O₂(g). Monomer and oligomeric species (ISO)1-8H⁺ were detected via online electrospray ionization mass spectrometry (ESI-MS) on the surface of pH ~ 2 water, and were then oxidized into a suite of products whose combined yields exceed ~ 5% of (ISO)1-8H⁺. MS/MS analysis revealed that products mainly consisted of alcohols, ketones, epoxides and acids. Our experiments demonstrated that olefins in ambient air may be oxidized upon impact on the surface of Fe-containing aqueous acidic media, such as those of typical to tropospheric aerosols.

Related experiments involving the reaction of ISO(g) with ·OH radicals from the photolysis of dissolved H₂O₂ were also carried out to test the surface oxidation of ISO(g) by photolyzing H₂O₂(aq) at 266 nm at various pH. The products were analyzed via online electrospray ionization mass spectrometry. Similar to our Fenton experiments, we detected (ISO)1-7H⁺ at pH < 4, and new m/z⁺ = 271 and m/z^- = 76 products at pH > 5.

Zooplankton - fish interaction in the littoral zone of Nyanza Gulf, Lake Victoria

The zooplankton community of the littoral zone of Nyanza Gulf, Lake Victoria, was studied between June 1998 and June 1999 to identify and quantify various zooplankton groups, and investigate the interactions that occur between them and the littoral fish through the food chain. Zooplankton samples were collected from five stations using a 83 micro-m mesh size plankton net hauled vertically through the water column. Fish samples were obtained by beach seine, except at Gingra (May 1999), where trawl samples were used. Gut/stomach analysis was carried out on the three major commercial species, Lates niloticus (L.), Oreochromis niloticus (L.) and Rastrineobola argentea (Pellegrin).

The significance of sedimentation and sediments to phytoplankton growth in drinking-water reservoirs

In the mesotrophic-eutrophic Saidenbach Reservoir in Saxony, the nanoplankton and cyanobacteria have increased at the expense of diatom dominance, due to a doubling of the external phosphorus load in the last 15 years. However, the phosphorus sedimentation flux is still very high (up to 80% of the input), corresponding to more than 2 g m2 d-1 in terms of dry weight. There is a strong correlation between the abundance of diatoms in the euphotic zone and their sedimentation flux (with a delay of about 2 weeks). Only about 25% of the deposited material could be clearly attributed to plankton biomass; the remainder resulted from flocculation and precipitation processes or directly from the inflow of clay minerals. The ash content of the deposited material was high (73%). Thus the sedimentation flux can be considered to operate as an internal water-treatment/oligotrophication process within the lake. The neighbouring Neunzehnhain Reservoir still has a very clear water with a transparency up to 18 m depth. Though the sediment was not much lower than Saidenbach sediment in total phosphorus and total numbers of bacteria, sulphide was always absent and the ratio of Fe 2+ to Fe 3+ was very low in the upper (0- 5 cm) layer. Thus the external and internal phosphorus loads do not attain the critical level necessary to induce a ”phosphorus - phytoplankton” feedback loop.

Rixton Clay Pits cSAC

This is the report on Habitats Directive, the Review of Consents Stage 1 and 2 by the Environment Agency of the Rixton Clay Pits cSAC. The Habitats Directive has the main aim to promote the maintenance of biodiversity by defining a common framework for the conservation of wild plants and animals and habitats of community interest. The Directive establishes a European ecological network known as "Natura 2000". The network comprises Special Areas of Conservation (SAC) and Special Protection Areas (SPA). In the section on Stage 1 or Screening Process of the Habitat Directive, it is identified the likely impacts upon the Rixton Clay Pits cSAC of a project, plan or activities, either alone or in combination with other projects, plans or activities, and considers whether these impacts are likely to be significant. In the section on Stage 2 or Appropiate Assessment of the Habitat Directive, it is considered the impact on the integrity of the Rixton Clay Pits cSAC of the projects, plans or activities, either alone or in combination with other projects, plans or activities, with respect to the site’s structure and function and its conservation objectives. Additionally, where these are adverse impacts, an assessment of the potential mitigation of those impacts. The criteria used in this report to identify relevant projects, plans or activities and their impacts are water quality discharge consents, waste management licences, abstraction licences, Integration Pollution Control (IPC) and Integrated Pollution Prevention Control (IPPC) permits. Proformas, hydrogeological and GIS maps are included in the review.

Biological survey: River Teign and tributaries with references to the discharge of ball clay wastes

This is the Biological survey of River Teign and tributaries with references to the discharge of ball clay wastes, document produced by South West Water Authority in 1973. This report focuses on on-site assessment of the benthic macro-invertebrates of the lower River Teign, River Bovey, Ugbrooke Stream and Blatchford Brook was undertaken on 19th and 22nd August 1977 to assess the effects of discharges from ball clay mining premises. Inspection of aquatic fauna in the field is of necessity, less extensive than laboratory identification of sorted samples, so that the resulting data underestimates the water quality. This is more pronounced in the Chandler Score than in the Trent Biotic Index which does not take account of species abundance. Chandler should thus be interpreted by the trends described rather than by absolute values calculated.

Biological survey of the River Teign and tributaries, with reference to the effect of ball clay discharges

This is the Biological survey of the River Teign and tributaries, with reference to the effect of ball clay discharges report produced by South West Water Authority in 1979. A survey of the macroinvertebrate riffle fauna in the Ball Clay mining area of the Bovey Basin, following a period of low rainfall, indicated that the River Bovey and the River Teign between Chudleigh and Teign Bridge, Newton Abbot were of good quality. Further downstream, the R. Teign and the lower reaches of the Ugbrooke Stream were identified as being of doubtful quality with the discharge from ECC Broadway continuing to give cause for concern.

Regulation of primary production in the Gulf of California through interaction of large-scale and local ocean processes [abstract]

EXTRACT (SEE PDF FOR FULL ABSTRACT): The suppression of primary productivity observed in eastern boundary ecosystems of the Pacific during El Nino episodes does not occur throughout the Gulf of California. On the contrary, analysis of the modern siliceous phytoplankton record from annually layered sediments and compilation of available primary productivity measurements indicate that production is significantly increased in the central Gulf during El Nino years compared to anti-El Nino years. Integrated observations of biological and physical variability during the spring of 1983, under the influence of the strong El Nino, show that very high primary productivity occurred along the eastern margin of the central Gulf. This resulted from the upwelling of a nutrient rich source provided by the locally formed Gulf water mass originating in the northern Gulf. Lower productivity and phytoplankton biomass were associated with the anomalous penetration of Tropical Surface Water along the western side of the Gulf.

A guide to the deep-water sponges of the Aleutian Island Archipelago

The first dedicated collections of deep-water (>80 m) sponges from the central Aleutian Islands revealed a rich fauna including 28 novel species and geographical range extensions for 53 others. Based on these collections and the published literature, we now confirm the presence of 125 species (or subspecies)of deep-water sponges in the Aleutian Islands. Clearly the deep-water sponge fauna of the Aleutian Islands is extraordinarily rich and largely understudied. Submersible observations revealed that sponges, rather than deep-water corals, are the dominant feature shaping benthic habitats in the region and that they provide important refuge habitat for many species of fish and invertebrates including juvenile rockfish (Sebastes spp.) and king crabs (Lithodes sp). Examination of video footage collected along 127 km of the seafloor further indicate that there are likely hundreds of species still uncollected from the region, and many unknown to science. Furthermore, sponges are extremely fragile and easily damaged by contact with fishing gear. High rates of fishery bycatch clearly indicate a strong interaction between existing fisheries and sponge habitat. Bycatch in fisheries and fisheries-independent surveys can be a major source of information on the location of the sponge fauna, but current monitoring programs are greatly hampered by the inability of deck personnel to identify bycatch. This guide contains detailed species descriptions for 112 sponges collected in Alaska, principally in the central Aleutian Islands. It addresses bycatch identification challenges by providing fisheries observers and scientists with the information necessary to adequately identify sponge fauna. Using that identification data, areas of high abundance can be mapped and the locations of indicator species of vulnerable marine ecosystems can be determined. The guide is also designed for use by scientists making observations of the fauna in situ with submersibles, including remotely operated vehicles and autonomous underwater vehicles.

Survey of plankton blooms and red tides and their interaction with environmental factors through monitoring satellite images

One of the most important marine ecological phenomena is red tide which is created by increasing of phytoplankton population, influenced by different factors such as climate condition changes, utrification hydrological factors and can leave sever and undesired ecological and economical effects behind itself in the case of durability. Coast line of Hormozgan is about 900km from east to west, within the range of geographical coordinates of 56 16 23.8, 26 58 8.8 to 54 34 5.33 and 26 34 32 eastern longitude and northern latitude, seven sampling stations were considered and sampled for a period of one year from October 2008 to October 2009. after the analysis of Satellite images, monthly, during the best time. In several stages, samplings were performed. In each station, three samples were collected for identification and determination of Bloom- creating species abundance. Cochlodinium polykrikoides was the species responsible for the discoloration which occurred at October 2008 in Hormozgan marine water. Environmental parameters such as sea surface temperature, pH, salinity, Dissolved Oxygen concentration, Total Dissolved Solids (T.D.S.), conductivity, nitrate, nitrite and phosphate and also chlorophyll a were measured and calculated. Kruscal Wallis test was used to compare the densities between different months, seasons and the studied stations. Mann-whitney test from Nonparametric Tests was used for couple comparison. Pearson correlation coefficient was used to determine the relationship between physical and chemical data set and the abundance of Cochlodinium polykrikoides. Multivariate Regression and analysis of variance (ANOVA) also were used to obtain the models and equations of red tide occurrence relationship, environmental parameters and nutrient data. The highest density was 26 million cells per liter in Qeshm station. A meaningful difference was observed between sampling months and seasons but there was no between sampling stations which indicates that in favorable conditions, the occurrence of this phenomenon by the studied species is probable. Regarding to β coefficients of nitrate, temperature, phosphate, Total Dissolvable Solutions (T.D.S) and pH these parameters are effective on the abundance of this species and red tide occurrence. Increase in these factors can represent the effects and outcomes of human activities and increase in marine pollution.

Faecal pellets in deep marine soft clay crusts: Implications for hot-oil pipeline design

In recent years, the presence of crusts within near surface sediments found in deep water locations off the west coast of Angola has been of interest to hot-oil pipeline designers. The origin for these crusts is considered to be of biological origin, based on the observation of thousands of faecal pellets in natural crust core samples. This paper presents the results of laboratory tests undertaken on natural and faecal pellet-only samples. These tests investigate the role faecal pellets play in modifying the gemechanical behaviour of clayey sediments. It is found that faecal pellets are able to significantly alter both the strength and the average grain-size of natural sediments, and therefore, influence the permeability and stiffness. Hot-oil pipelines self-embed into and subsequent shear on crusts containing faecal pellets. Being able to predict the time required for installed pipelines to consolidate the underlying sediment and thus, how soon after pipe-laying, the interface strength will develop is of great interest to pipeline designers. It is concluded from wet-sieving samples before and after oedometer tests, that the process of pipe laying is unlikely to destroy pellets. They will therefore, be a major constituent of the sediment subject to soil-pipeline shearing behaviour during axial pipe-walking and lateral buckling. Based on the presented results, a discussion highlighting the key implications for pipeline design is therefore provided. Copyright © 2011 by ASME.

A new apparatus for modelling excavations

Underground space is commonly exploited both to maximise the utility of costly land in urban development and to reduce the vertical load acting on the ground. Deep excavations are carried out to construct various types of underground infrastructure such as deep basements, subways and service tunnels. Although the soil response to excavation is known in principle, designers lack practical calculation methods for predicting both short- and long-term ground movements. As the understanding of how soil behaves around an excavation in both the short and long term is insufficient and usually empirical, the judgements used in design are also empirical and serious accidents are common. To gain a better understanding of the mechanisms involved in soil excavation, a new apparatus for the centrifuge model testing of deep excavations in soft clay has been developed. This apparatus simulates the field construction sequence of a multi-propped retaining wall during centrifuge flight. A comparison is given between the new technique and the previously used method of draining heavy fluid to simulate excavation in a centrifuge model. The new system has the benefit of giving the correct initial ground conditions before excavation and the proper earth pressure distribution on the retaining structures during excavation, whereas heavy fluid only gives an earth pressure coefficient of unity and is unable to capture any changes in the earth pressure coefficient of soil inside the zone of excavation, for example owing to wall movements. Settlements of the ground surface, changes in pore water pressure, variations in earth pressure, prop forces and bending moments in the retaining wall are all monitored during excavation. Furthermore, digital images taken of a cross-section during the test are analysed using particle image velocimetry to illustrate ground deformation and soil-structure interaction mechanisms. The significance of these observations is discussed.

The nature and origin of deep ocean clay crust from the Gulf of Guinea

Deep ocean sediments off the west coast of Africa exhibit a peculiar undrained strength profile in the form of a crust, albeit of exceptionally high water content, overlying normally consolidated clay. Hot-oil pipelines are installed into these crustal sediments, so their origins and characteristics are of great interest to pipeline designers. This paper provides evidence for the presence of burrowing invertebrates in crust material, and for the way sediment properties are modified through their creation of burrows, and through the deposition of faecal pellets. A variety of imaging techniques are used to make these connections, including photography, scanning electron microscopy and X-ray computer tomography. However, the essential investigative technology is simply the wet-sieving of natural cores, which reveals that up to 60% by dry mass of the crustal material can consist of smooth, highly regular, sand-sized capsules that have been identified as the faecal pellets of invertebrates such as polychaetes. Mechanical tests reveal that these pellets are quite robust under effective stresses of the order of 10 kPa, acting like sand grains within a matrix of fines. Their abundance correlates closely with the measured strength of the crust. While this can easily be accepted in the context of a pellet fraction as high as 60%, the question arises how a smaller proportion of pellets, such as 20%, is apparently able to enhance significantly the strength of a sediment that otherwise appears to be normally consolidated. A hypothesis is suggested based on the composition of the matrix of fines around the pellets. These appear to consist of agglomerates of clay platelets, which may be the result of the breakdown of pellets by other organisms. Their continued degradation at depths in excess of 1 m is taken to explain the progressive loss of crustal strength thereafter.

Development of a new apparatus for modeling deep excavation related problems in geotechnical centrifuge

Underground space is commonly exploited both to maximise the utility of costly land in urban development and to reduce the vertical load acting on the ground. Deep excavations are carried out to construct various types of underground infrastructure such as deep basements, subways and service tunnels. Although the soil response to excavation is known in principle, designers lack practical calculation methods for predicting both short- and long-term ground movements. As the understanding of how soil behaves around an excavation in both the short and long term is insufficient and usually empirical, the judgements used in design are also empirical and serious accidents are common. To gain a better understanding of the mechanisms involved in soil excavation, a new apparatus for the centrifuge model testing of deep excavations in soft clay has been developed. This apparatus simulates the field construction sequence of a multi-propped retaining wall during centrifuge flight. A comparison is given between the new technique and the previously used method of draining heavy fluid to simulate excavation in a centrifuge model. The new system has the benefit of giving the correct initial ground conditions before excavation and the proper earth pressure distribution on the retaining structures during excavation, whereas heavy fluid only gives an earth pressure coefficient of unity and is unable to capture any changes in the earth pressure coefficient of soil inside the zone of excavation, for example owing to wall movements. Settlements of the ground surface, changes in pore water pressure, variations in earth pressure, prop forces and bending moments in the retaining wall are all monitored during excavation. Furthermore, digital images taken of a cross-section during the test are analysed using particle image velocimetry to illustrate ground deformation and soil–structure interaction mechanisms. The significance of these observations is discussed.