Since the UK industrial revolution, coal combustion, ore smelting and other industrial activities have resulted in a marked increase in emissions of potentially toxic elements (PTEs) such as antimony (Sb), lead (Pb), arsenic (As), copper (Cu) and zinc (Zn), along with polycyclic aromatic hydrocarbons (PAHs), to the atmosphere. Although stricter environmental regulation and improved technology has led to a notable decline for some contaminant emissions in recent decades, this has not been observed for all elements, e.g. Sb, where only a modest reduction in emissions have been recorded. Once emitted, Sb along with Pb, As, Cu, Zn and PAHs may persist in the environment for considerable periods of time after their release; although their chemical associations may change, elements are not broken down over time and organic contaminants may break down slowly. Above all, PTEs and PAHs are detrimental to human and environmental health, with chemical forms of Sb, Pb, As and PAHs categorised as carcinogenic. Understanding their behaviour and fate in the environment is therefore an important step towards evaluating their likely impact on both ecosystem and human health. Consequently, this study focuses on the release, behaviour and fate of contaminants from current and past anthropogenic sources in the urban and rural environment, with a specific interest in Sb and PAHs, where emissions originate from similar anthropogenic sources, with Pb, As, Cu and Zn also included for comparison purposes. Current and past industrial activity was identified as the dominant source of PTEs and PAHs to the urban environment, with emissions from vehicle, coal combustion and metal smelting identified as main contributors to total contaminant concentrations. Using road dust collected from Edinburgh at five high- and low-traffic roads at a distance of 10 and 50 m from the closest road junction, concentrations of Sb, Pb, Cu, Zn, PAHs and Pb isotope ratios were determined, with road dust undergoing further characterisation using chemical (sequential extraction) and spectroscopic (X-ray diffraction, SEM-EDX) techniques. No consistent trend for the element concentrations released from vehicles braking at 10 and 50 m from the closest road junction was observed. Mean concentrations for Sb, Cu and Zn were 5.3 ± 2.8 mg kg-1, 91.4 ± 48 mg kg-1 and 237 ± 144 mg kg-1, respectively, and were similar to road dust sampled from five high- and five low-traffic locations in Glasgow (Sb 4.5 ± 2.1 mg kg-1; Cu 117 ± 71.9 mg kg-1; Zn: 283 ± 146 mg kg-1). This was in contrast to mean concentrations for Pb and Σ16PAHs obtained from Glasgow (Pb 250 ± 283 mg kg-1, Σ16PAH 7.7 ± 4.3 mg kg-1) where values were approximately double and two-thirds greater than those found in Edinburgh (Pb 135 ± 129 mg kg-1, Σ16PAH 4.7 ± 2.9 mg kg-1), respectively. Lead isotopic analysis of Glasgow road dust (206Pb/207Pb range of 1.140-1.174) showed a strong influence of past emissions from coal combustion and metal smelting, and was in agreement with Glasgow's industrial history. For Edinburgh, the isotopic signature was considerably lower (206Pb/207Pb range of 1.116-1.151), and was influenced moreso by emissions of Australian sourced Pb in leaded fuel. Isotopic signatures in Edinburgh were lowest at easterly locations within 5 km of Edinburgh airport (206Pb/207Pb ~ 1.12), and corresponded with past vehicle emissions from leaded petrol use, and to a lesser degree, emissions from avgas, which was consistent with the mean annual wind direction for Edinburgh. The mobility of elements from the road dust to the aqueous phase were assessed by sequential extraction, and by using road surface water samples which showed mobility decreased in the order of Zn > Cu > Pb > Sb. Road dust characterised by XRD and SEM-EDX had a high proportion of quartz present (~55%), whilst the presence of less abundant minerals such as calcite were found to increase Pb mobility through ease of dissolution into the aqueous phase. For the rural environment, the behaviour and fate of elemental pollution originating from two former mining sites, an Sb mine at Glendinning, SW Scotland, and a Pb mine at Tyndrum in central Scotland was examined. Under specific environmental conditions, Sb was found to be both mobile and immobile in the environment. The chemical weathering of stibnite found in spoil heaps at Glendinning Sb mine demonstrated that ~3% of total Sb can be mobilised during the chemical weathering process, while hydrous Fe oxides and organic matter in the surrounding soil favoured its retention. The retention of Sb, along with Pb, was similarly observed in Loch Tay sediment downstream of Tyndrum Pb mine, where upon deposition, Sb and Pb remained immobile in sediment and allowed the construction of deposition chronologies for two sediment cores to be established. Excellent agreement between the sediment core deposition chronologies was observed, with both chronologies identifying atmospheric deposition as the primary source of Sb to Loch Tay sediment, whilst the dominant source of Pb was from Tyndrum Pb mine ~25 km upstream of Loch Tay. Relative to Sb and Pb, As had the greatest mobility, with its geochemical behaviour and partial retention by the solid phase influenced by the presence of Fe. This was evident in the surrounding soil at Glendinning Sb mine, where As was associated with hydrous Fe oxides present in the solid phase, while at Loch Tay, the redox cycling of Fe resulted in the post-depositional mobility of As in sediment. The use of ombrotrophic peat bogs for this study provided an effective means to assess atmospheric deposition of contaminants over past centuries; they continually accumulate and receive all their nutrients and contaminants exclusively by deposition from the atmosphere. The deposition archives of Sb and Pb from two Scottish peat cores sampled from Great Moss, Cairngorms Mountains, and, Auchencorth Moss, Midlothian, were used to construct chronologies for historic and contemporary emissions, particularly in relation to current and historic anthropogenic activities observed in urban and rural environments. At Great Moss, the deposition of Sb and Pb during the 19th century increased by a factor of 10 and 4, respectively, as a result of the industrial revolution and emissions from the combustion of coal and metal smelting. The trend continued into the 20th century where Sb and Pb deposition peaked ~1950, followed by a decline towards the early 21st century by a factor of 5 and 11, respectively. Over this period of time, the contribution from coal combustion and metal smelting towards total anthropogenic emissions was on the decline, while emissions from the combustion of leaded fuel increased until the ~1980s. Although deposition chronologies before 1970 for Sb and Pb at Auchencorth Moss were generally in agreement with those from Great Moss, several differences were observed after 1970, or more specifically, in the top ~10 cm of the peat core. This was a result of sub-surface perturbations for Ti, Sb, Pb and 210Pb concentrations, and indicated once deposited, elements were susceptible to post-depositional mobility brought about from a change in environmental conditions. The thicker acrotelm layer present at Auchencorth Moss, and the vertical movement of the peat water-table within this layer, resulted in a change in redox conditions and led to the redox cycling of Mn and Fe, which in turn, influenced vertical concentrations of Ti, Sb, Pb and 210Pb. While Sb and Pb are usually found immobile in peat systems, the post-deposition mobility of Sb and Pb at Auchencorth Moss was comparable to a peat core sampled from Flanders Moss, and indicated that under specific environmental conditions, both elements can become mobile in ombrotrophic peat bogs. It is worth bearing in mind however, that these results are the exception, and in all other cases ombrotrophic peat bogs remain a reliable archival material to use.

Benzene and toluene are known groundwater contaminants . Male CD-I mice were continuously exposed to 0, 31, 166, and 790 mg/ L benzene and 0, 17, 80, and 405 mg/L toluene, respectively, in drinking water for four weeks. Benzene caused a reduction of leukocytes, lymphocytes and erythrocytes, and resulted in a macrocytic anemia. Lymphocyte response to both B- and T-cell mitogens, mixed lymphocyte response to alloantigens, and the ability of cytotoxic lymphocytes to lyse tumor cells were enhanced at the lowest dose of benzene and depressed in the higher dosage animals. Benzene at doses of 166 and 790 mg/L decreased the number of sheep red blood cell (SRBC) -specific plaque-forming cells, the level of serum anti-SRBC antibody, and the activity of interleukin-2 (IL -2). Benzene treatment increased endogenous concentrations of the brain biogenic amines norepinephrine (NE), dopamine (DA) and serotonin (5-HT), and concomitantly, elevated the levels of their respective major metabolites vanillymandelic acid (VMA), 3,4-dihydroxyphenyl acetic acid (DOPAC) and homovanillic acid (HVA), and 5-hydroxyindoleacetic acid (5-HIAA), in several brain regions . In most cases, the changes were dose related; in several instances, maximum effects occurred at the 166 mg/L benzene dose. Toluene did not adversely affect the hematological parameters. Depression of immune function was evident at the highest dose (405 mg/L), except for mitogeneses. Increased neurochemical concentrations caused by toluene displayed a dose-dependent biphasic manner which began at a dose of 17 mg/L, peaked at 80 mg/L, and decreased at 405 mg/L. Toluene treatment had more selective effects on NE, 5-HT ,VMA and 5-HIAA, than DA, DOPAC and HVA. Both compounds, by increasing concentrations of the hypothalamic NE and its major metabolite VMA, stimulated the hypothalamic-pituitary-adrenocortical axis activity, resulting in an elevated plasma adrenocorticotropic hormone and serum corticosterone which had an additive adverse effect on IL-2 synthesis. Toluene, 325 mg/ L, completely inhibited benzene-induced cytopenia and immunosuppression when it was coadministered with benzene (166 mg/L). The low dose of toluene (80 mg/L ) did not antagonize benzene immunotoxicity. Mice given the combined exposures exhibited raised levels of regional neurochemicals when compared to the untreated controls. Increased levels of monoamine metabolites in several brain regions were greater in the combined treatments of benzene and toluene than when either chemical was used alone. The results of the interaction studies support the known metabolic interaction mechanisms of benzene and toluene.

Background: The synthetic insecticide DDT (dichlorodiphenyltrichloroethane) has been speculated to increase breast cancer risk due to its environmental persistence, levels of bioaccumulation in breast adipose tissue, and endocrine disrupting actions. Epidemiological studies have had inconsistent findings, however a study in MMTV-neu mice determined that localized, developmental exposure to the reported anti-androgen p,p' DDE accelerated mammary tumor development. This study tested the potential cancer-promoting actions of p,p' DDE, the most prevalent and persistent DDT metabolite. <br>Objectives: To identify and characterize the expression of p,p' DDE -regulated genes to determine how developmental exposure may influence mammary tissue to promote tumor formation. Methods: For localized delivery, ELVAX 40P pellets containing various doses of p,p' DDE, hydroxyflutamide (another anti-androgen), and mixtures of p,p' DDE with other congeners like o,p' DDE and p,p' DDT were implanted into the mammary fatpads of prepubertal female mice. p,p' DDE-regulated genes were identified by microarray analysis and analyzed by real time RT-PCR. <br>Results: Lipid-adjusted levels of p,p' DDE in mammary adipose tissue and serum in young mice were within the ranges of human exposure. p,p' DDE significantly upregulated casein gamma (csn1s2a ), keratin 18 (krt18) and interferon-induced protein 44 (ifi44) genes in mammary tissue. These genes were similarly, but not significantly regulated by hydroxyflutamide. The dose of p,p' DDE that caused early tumor onset in a previous study resulted in unique expression for all three genes and concentrations of p,p' DDE also influenced gene responses for the mixtures. However, no qualitative changes were observed in gland morphology. Significant upregulation of transforming growth factor beta (tgfb1) and downregulation of interleukin 10 (il10) in splenic leukocytes indicated that localized delivery of p,p' DDE to the mammary gland also influences systemic immune responses. Significant upregulation of il10 by p,p' DDE and hydroxyflutamide suggest that some of p,p' DDE actions may be through its anti-androgenic activity. <br>Conclusions: Relevant human exposure levels of p,p' DDE induce significant increases in expression of csn1s2a, krt18 and ifi44. This activity as well as those induced by other doses, ratios and hydroxyflutamide suggest p,p' DDE actions may involve anti-androgenic activity and influence local and systemic effects in a HER2+ breast cancer mouse model. / Mylan School of Pharmacy and the Graduate School of Pharmaceutical Sciences / Pharmacology-Toxicology / PhD / Dissertation

It is estimated that 22 000 contaminated areas exist in Sweden today. In order to classify the risk of contaminant migration from these areas and to prioritize which of these contaminated areas should first be treated, the Swedish Environmental Protection Agency (EPA) has designed a method, for the investigation of contaminated areas (MIFO). One of these contaminated areas is the landfill Gräsötippen outside Köping. The landfill has been used by both Yara AB and the Köping municipality between the years 1945 and 1975, and both industrial and household waste have been deposited there. The aim of this report is to survey which contaminants that can be found in the soil and water in the landfill Gräsötippen and to evaluate the migration of these contaminants. With help of this information, the landfill will then be risk classified according to MIFO. The goal is that this report will provide a basis for future studies and remedial measures at the landfill. To get a picture of what has been deposited at the landfill Gräsötippen, employees and former employees at Yara and others with connection to the landfill have been interviewed. Piezometers have been installed in and around the landfill so as to provide information on groundwater levels and movement, and for the collection of groundwater samples. Soils samples were collected as well. The water and soil samples were analyzed with regard to metals, organic compounds and nutrients. Furthermore, groundwater flow has been modeled using VS2DI, in order to get a picture of the groundwater’s flow direction and velocity under the landfill. In the water samples, only lead was detected with levels over the Maximum Contaminant Level (MCL) from the EPA. Relatively high levels of nutrients were also detected. In the soil, carcinogenic PAH, PCB, aliphatic hydrocarbons, aromatic hydrocarbons, arsenic, lead, cadmium, mercury and zinc were detected over the EPA MCL. The landfill Gräsötippen has a good location in an area with deep clay, which prevents rapid spreading of contaminants. No high levels of contaminants are leaching out today. The spreading of the contaminants is minor; most of the contaminants are fixed in the soil and do not spread to the surroundings. The water flow’s primary direction from the landfill is south but there are also flows to the west and east. Today, there are a number of proposals with regard to decreasing the risk for future contaminant dispersal from the landfill and to keep control of the water that is used in the area. A few of these proposals are to finally cover the landfill, to analyze the grass and plants in the enclosed pasture on the landfill, and to continuously analyze the water in the installed piezometers and drinking water wells on and around the landfill. The landfill Gräsötippen is classified to risk class 3, moderate risk, according to MIFO. / Det uppskattas idag finnas 22 000 förorenade områden i Sverige. För att kunna riskklassa dessa förorenade områden och prioritera vilka som först bör efterbehandlas har Naturvårdsverket utarbetat en Metodik för Inventering av Förorenade Områden (MIFO). Gräsötippen utanför Köping är ett av dessa förorenade områden. Deponin har använts av både Yara AB och Köpings kommun mellan åren 1945-1975 och fungerat som deponi för både industri- och hushållsavfall. Syftet med denna rapport är att kartlägga vilka föroreningar som finns i mark och vatten i Gräsötippen och tolka föroreningarnas spridning. Utifrån den informationen ska deponin sedan riskklassas enligt MIFO. Målet är att rapporten ska kunna fungera som underlag för framtida åtgärdsplaner för Gräsötippen. För att få en bild över vad som har deponerats på Gräsötippen har anställda och före detta anställda vid Yara samt andra som har haft anknytning till Gräsötippen intervjuats. Grundvattenrör har installerats i och runtom deponin för att det skulle kunna tolkas hur grundvattnet rör sig under deponin och för att det skulle kunna tas prover på grundvattnet och jorden. De vatten- och jordprover som togs, analyserades med avseende på metaller, organiska föreningar och närsalter. Dessutom har en modellering utförts i VS2DI för att få en bild över grundvattnets flödesriktning och hastighet under deponin. I vattenproven detekterades endast bly över Naturvårdsverkets riktvärde samt relativt höga halter av närsalter. I jorden detekterades cancerogena PAHer, PCB, alifater, aromater, arsenik, bly, kadmium, kvicksilver och zink över Naturvårdsverkets riktvärden. Gräsötippen är bra placerad i ett område med tjock lera som förhindrar snabb spridning och idag lakas inga höga halter av föroreningar ut. Spridningen av föroreningar är liten, istället ligger de flesta föroreningarna fast i marken och sprids därmed inte till omgivningen. Vattenflödets huvudriktning från deponin är söderut, men det sker även flöden åt både väster och öster. Det finns i dagens läge en del förslag på åtgärder som bör utföras på Gräsötippen för att minska risken för framtida spridning och upprätthålla kontroll på det vatten som används i närområdet. Några av dessa åtgärder är att sluttäcka deponin, att analysera gräs och växter i hagen på deponin samt att kontinuerligt analysera vattnet i grundvattenrören och brunnarna på och runt Gräsötippen. Vid riskklassningen av Gräsötippen enligt MIFO, klassas den till riskklass 3, måttlig risk.

Contaminants in aqueous environments exist in phases that are sorbed to suspended or colloidal material and that are dissolved in solution. Polymer flocculants can be used to remove suspended or colloidal material along with sorbed contaminants, but they remove little of the dissolved contaminants. In the study presented here, development of polymers to sorb contaminants from aqueous solution during the flocculation process was investigated. Atrazine and phosphate (H₂PO₄ ̄) were chosen as test contaminants. For a given test contaminant, multiple copies of a functional group that interacted with that contaminant were inserted into the polymer backbone of a polyacrylamide flocculant. The functional groups inserted into the polymer structure acted as a trap for the dissolved contaminant. The traps were a cyclic secondary amine that interacted with atrazine, and a thiourea that interacted with phosphate. Modified flocculants with different configurations and densities of trapping groups were made and evaluated for removal of the test contaminants from aqueous suspensions. The suspensions consisted of bentonite or kaolinite in water with a known concentration of a test contaminant. The atrazine source was labeled with ¹⁴C and concentrations were measured using a scintillation counter. The source of phosphate used was NaH₂PO₄ and ion chromatography was used to measure the aqueous concentrations of phosphate. In general, the modified polymer flocculants containing trapping groups removed significantly more atrazine and phosphate from suspension compared to the control polymer flocculants ([alpha] =0.05). While the amount of modified polymers needed to achieve significant removal of the test contaminant were higher than the Environmental Protection Agency limit for concentration of polyacrylamide flocculants in water, it was possible to enhance the polymers sorbtion and removal of contaminants from solution during the flocculation process.

Objectives To evaluate the association between exposures to the main chemical contaminants released by the industry in freshwater and the rise in cancer cases among the population in China. Methods A systematic review was undertaken of the scientific literature compiled in the MEDLINE (via PubMed©), Google scholar, Web of Knowledge. The descriptors used were "cancer", "water pollution”, “industry” and “chemical", limited to studies that relevant to the research questions. Articles selected were of any type in English, from the inception of the indexing of the primary source until July 28th of 2013. With the quantitative data, Health impact assessment formulas are developed and then applied to subsequent data to make estimate. Results The search generated 306 articles, from which 10 were selected after applying the inclusion and exclusion criteria. The analysis of freshwater contaminants that attributed to industry in this review included aromatic amine, vinyl chloride, benzene, hexavalent Chromium, dioxin, and others of industrial origin. The majority of the studies find a significant link between exposure to drinking water contaminants and the increase in cancer cases, especially in the rural areas. In some of the studied populations a significant dose-response relationship was observed. Discussion After reviewing the included studies and the estimation of health impact assessment, I concluded that the association between cancer risks and industrial contamination in freshwater resources in China does indeed exist. While there are several other factors that interact the cancer risks, such as agriculture related water pollution and rapid growth of population. Taking into account that most of the articles were located in western countries, more Chinese studies are required in order to know the effect of freshwater contamination on cancer risks, in particular among those who lived in rural industry area. Conclusion This study provides the first estimated health impacts based on the relationship between industrial freshwater pollution and cancer risks, supporting decision makers to formulate public health recommendations to ensure a safer and healthier environment in the future. However, further study is critically needed for the prevention of this form of contamination. / published_or_final_version / Public Health / Master / Master of Public Health

This thesis explored new methods for understanding the fate and transport of halogenated organic contaminants in the environment. A theoretical method of hazard assessment of chemical mixtures containing large numbers of components was developed and its application illustrated using polychlorinated alkanes, toxaphene, and halogenated dibenzo-para-dioxins and furans. Partitioning properties predicted by high-throughput quantitative structure property relationships were used to locate mixture constituents on plots displaying equilibrium phase distribution in various environmental compartments and the potential for bioaccumulation and long range transport. Potentially hazardous components were identified graphically for more detailed assessments. The applicability of XAD-resin based passive air samplers (XAD-PAS) for studying neutral polyfluoroalkyl substances (nPFAS) in the atmosphere was tested empirically. XAD-PASs have sufficiently high uptake capacity to yield temporally averaged nPFAS concentrations over period as long as a year. When applied as part of the Global Atmospheric Passive Sampling network, nPFAS were found to be truly global contaminants.

An assessment of the groundwater quality at the Olusosun landfill in Lagos, Nigeria was conducted to determine interactions between the landfill wastes and the groundwater and the potential migration of pollutants into the neighbouring communities. Groundwater samples were collected from four locations within the landfill bi-weekly for three months (March 19, 2013 to May 28, 2013), and analysed for water quality parameters and metals. The results indicated that the concentrations of some metals (Cr, Fe, Cd, Mn, and Co) and other water quality parameters in some sampling locations were slightly above the World Health Organization (WHO) and the Nigerian Standard for Drinking Water Quality (NSDWQ) standard limits. Lead was also detected in the groundwater samples, though at concentrations within the standard limits. Conclusively, the Olusosun landfill has impaired groundwater quality, thereby, posing environmental and human health concerns to the neighbouring communities of Oregun, Ketu and Ojota.

This thesis explored new methods for understanding the fate and transport of halogenated organic contaminants in the environment. A theoretical method of hazard assessment of chemical mixtures containing large numbers of components was developed and its application illustrated using polychlorinated alkanes, toxaphene, and halogenated dibenzo-para-dioxins and furans. Partitioning properties predicted by high-throughput quantitative structure property relationships were used to locate mixture constituents on plots displaying equilibrium phase distribution in various environmental compartments and the potential for bioaccumulation and long range transport. Potentially hazardous components were identified graphically for more detailed assessments. The applicability of XAD-resin based passive air samplers (XAD-PAS) for studying neutral polyfluoroalkyl substances (nPFAS) in the atmosphere was tested empirically. XAD-PASs have sufficiently high uptake capacity to yield temporally averaged nPFAS concentrations over period as long as a year. When applied as part of the Global Atmospheric Passive Sampling network, nPFAS were found to be truly global contaminants.

No description available.