The relationship between soils, soil water and stream chemistry was investigated for a first order stream in a small forested watershed in the southern Laurentians, Quebec. The study was restricted to near-stream processes, particularly how the chemistry of water leaving a hillslope influenced stream chemistry. For snowmelt, 1986, a number of naturally occurring chemical elements were used to separate stream flow into three subsurface flowpaths: groundwater, solum and upwelling flow. By quantifying upwelling flow, we introduced a new approach to identify solutions forced from the groundwater up through the solum before entering the channel. In upwelling flow, we found that dissolved silicon was reactive and total aluminum, monomeric aluminum, hydronium, magnesium and fluoride were non-reactive. For spring storms, 1992, we used an end member mixing approach to describe streamwater as a combination of chemically distinct solutions from different depths in the soil. Solutions were defined by concentrations of calcium, magnesium, sodium and dissolved silicon. The contributions of water from each soil depth were estimated using the variations in end member chemistry that were measured during the storms. Hydrological reconstructions of the events were possible and it was found that the contribution of water from each depth in podzols is related to the height of the water table in the near-stream soils.

Denna avhandling behandlar den småskaliga rumsliga variationen av löst organiskt kol (DOC, engelsk term: dissolved organic carbon), dess koncentration, masstransport och karaktär, i bäckar inom två barrskogsbeklädda avrinningsområden (delavrinningsområden 0,01-78 km²). Provtagningen gjordes uppströms och nedströms varje bäckförgrening under sommarbasflöde. Koncentrationen av DOC varierade inom en tiopotens (4-66 mg/l), liksom flera andra kemiska parametrar. Vid riksinventeringen av vattendrag för 2000 i norra Sverige noterades en snarlik spännvidd. Enligt Naturvårdverkets bedömningsgrunder för sjöar och vattendrag återfanns alla tillståndsklasser för DOC och pH, samt mänsklig påverkansgrad till försurningen inom de två studerade områdena. Den specifika avrinningen (flöde per areaenhet) varierade kraftigt i källflödena och inverkade på deras bidrag till kemin nedströms. Vattenkemin och specifika avrinningen var stabila i delavrinningsområden större än 15 km². Det kan vara nödvändigt att provta så stora områden om generella värden för landskapet önskas, men källflödenas kemi kommer då inte att kunna karakteriseras, ehuru källflödena utgör den största delen av bäcksträckan och det akvatiska ekosystemet. Nedströms är DOC-koncentrationen, och många andra kemiska parametrar, lika med summan av bidragen från källflödena och nedströms utspädning av inflödande vatten. Tillkommer gör processer inom bäcken och vattnets utbyte med botten/grundvatten (den hyporheiska zonen), men även DOC-förluster/transformationer vid vissa bäckförgreningar och sjöar. Ovanstående resonemang förklarade bäckvattenkemins minskande variation och vanligen lägre DOC-koncentrationer nedströms i ett landskapsperspektiv. Längs bäcksträckorna observerades ingen generell minskning av DOC-koncentration eller ändring av dess karaktär. Skillnaden i DOC-koncentration och relaterade parametrar mellan källflöden och nedströms styrdes i hög grad av vilka landskapselement (myrar, sjöar och skogsmark) som vattnet hade passerat innan det hamnade i bäckarna, samt samspelseffekter med den specifik avrinningen och platserna med DOC-förlust. Prognoser med multivariata modeller baserade på kartinformation testades men kunde inte förutsäga det rumsliga mönstret eller DOC-koncentrationen med erforderlig precision. Lämpliga rutiner inom miljöövervakningen för att övervaka den rumsliga variationen av kemin i ytvatten saknas alltjämt. Vid planering av terrestra och akvatiska skötselåtgärder bör man beakta bäckvattnets naturliga kemiska variation. / This thesis quantifies the small-scale spatial variation of dissolved organic carbon (DOC) concentrations, fluxes and character in two boreal catchments (subcatchments 0.01-78 km²) using ”snapshots” of summer base flow where samples were taken upstream and downstream from every node in the stream network. An order of magnitude variation was found in DOC-concentrations, and many other chemical parameters. The range was similar to that found in all of northern Sweden by the national stream survey in 2000. According to the official assessment tools used in Sweden, the entire range of environmental status for DOC, pH and human acidification influence existed within these two study catchments. A large variability in specific discharge had a major impact on the contribution of headwaters to downstream chemistry. The water chemistry parameters were relatively stable at catchment areas greater than 15 km². Sampling at that scale may be adequate if generalised values for the landscape are desired. However the chemistry of headwaters, where much of the stream length and aquatic ecosystem is found would not be characterized. Downstream DOC-concentrations, as well as many other chemical parameters, are the sum of headwater inputs, in combination with progressive downstream dilution by inflowing water with its own DOC-concentration and character. Superimposed upon this are in-stream and hyporheic processes, as well as discrete loci of DOC loss/transformation at lakes and stream junctions. At the landscape scale, this results in a decreased downstream variation in stream water chemistry and often, but not necessarily, lower average DOC-concentrations. Along stream reaches there was not a loss of DOC-concentration or a consistent change in character. While the importance of in-stream/hyporheic processes that consistently alter DOC-concentrations along the channel network cannot be ruled out, the differences between headwater and downstream DOC-concentrations and related parameters depend largely on the mosaic of landscape elements (mires, lakes and forest soil) contributing water to the channel network, combined with patterns of specific discharge and discrete loci of DOC loss. Assessment would be facilitated by map information that could predict spatial patterns. Multivariate models using maps, however, did not give satisfactory predictions. Appropriate procedures for dealing with spatial variation in the environmental assessment of surface waters are not yet established. An awareness of stream water chemistry’s natural spatial variability should be considered when planning aquatic and terrestrial management.

In this thesis, the implementation and results of studies into the effect of pH on the kinetics of various iron transformations in natural waters are described. Specific studies include i) the oxidation of Fe(II) in the absence and presence of both model and natural organic ligands, ii) the complexation of Fe(III) by model organic compounds, and iii) the precipitation of Fe(III) through the use of both laboratory investigations of iron species and kinetic modeling. In the absence of organic ligands, oxidation of nanomolar concentrations of Fe(II) over the pH range 6.0 -- 8.0 is predominantly controlled by the reaction of Fe(II) with oxygen and with superoxide while the disproportionation of superoxide appears to be negligible. Oxidation of Fe(II) by hydrogen peroxide, back reduction of Fe(III) by superoxide and precipitation of Fe(III) have been shown to exert some influences at various stages of the oxidation at different pH and initial Fe(II) concentrations. In the presence of organic ligands, different effects on the Fe(II) oxidation kinetics is shown with different organic ligands, their initial concentrations and with varying pH. A detailed kinetic model is developed and shown to adequately describe the kinetics of Fe(II) oxidation in the absence and presence of various ligands over a range of concentrations and pH. The applicability of the previous oxidation models to describe the experimental data is assessed. Rate constants for formation of Fe(III) by a range of model organic compounds over the pH range 6.0 -- 9.5 are determined. Variation of rate constants for Fe(III) complexation by desferrioxamine B and ethylenediaminetetraacetate with varying pH is explained by an outer-sphere complexation model. The significant variation in rate constants of Fe(III) complexation by salicylate, 5-sulfosalicylate, citrate and 3,4-dihydroxylbenzoate with varying pH is possibly due to the presence of different complexes at different pH. The results of this study demonstrate that organic ligands from different sources may influence the speciation of iron in vastly different ways. The kinetics of Fe(III) precipitation are investigated in bicarbonate solutions over the pH range 6.0 -- 9.5. The rate of precipitation varies by nearly two orders of magnitude with a maximum rate constant at a pH of around 8.0. The results of the study support the existence of the dissolved neutral species Fe(OH)30 and suggests that it is the dominant precursor in Fe(III) polymerization and subsequent precipitation at circumneutral pH. Variation in the precipitation rate constant over the pH range considered is consistent with a mechanism in which the kinetics of iron precipitation are controlled by rates of water exchange in dissolved iron hydrolysis species.

Mire pools – shallow water-bodies in peat-forming wetlands – are a characteristic feature of New Zealand’s subalpine and alpine landscapes (>1000 m a.s.l.), yet have been the subject of few biological studies to date, particularly of their algal communities. This research focuses on these subalpine systems, and on their diatom communities. Despite the established paradigm of ubiquitous dispersal in micro-organisms, recent taxonomic studies have confirmed a distinctive endemic component in the freshwater diatom flora of the New Zealand / Tasmania / East Australian region. In this study, I examined benthic diatom communities from >320 freshwater sites throughout New Zealand and showed that over 20% of species may be confined to this region. The endemic diatom species had highest densities in stable, unproductive environments, particularly in high-altitude mire pools and tarns. In most cases, non-endemic taxa coexisted with endemic species. This raised questions about (1) the special characteristics of mire pools and tarns (since endemism might be expected in areas that have unique environmental characteristics), and (2) the mechanisms that have allowed existing endemic taxa to withstand displacement by common cosmopolitan taxa, which, by definition, are successful colonisers. I addressed these questions using two years of data from four subalpine mire pools (Bealey Spur wetland, near Arthur’s Pass, South Island). Physico-chemical data showed that water chemistry of these pools may differ from that of many Northern Hemisphere mire systems with respect to the relationship between pH and dissolved ions (especially calcium). This may be due to a combination of high pH rainfall, high rainfall quantities that limit the acidification effects of humic substances, and possibly vegetation differences. Therefore, some endemic taxa may be confined to these habitats because of the characteristic properties of the pools. I investigated the effects of disturbances in these stable environments. In the largest pool endemic species were shown to decline as wind-induced substrate disturbance increased. Endemic species also declined in two pools following small-scale experimental substrate disturbances. In all cases, non-endemic species remained unchanged. The distinctive species Eunophora cf. oberonica was responsible for much of the observed decline in endemic species abundances, which was evidently due to destruction of their specialised habitat within the cyanobacterial mats that made up the pool substrates. I explained pool-specific responses of diatom communities to disturbances by drawing on recent theory of invasibility as an intrinsic environmental property. I further investigated species coexistence by examining several general patterns of interspecific coexistence described for macroscopic organisms (e.g., abundance – occupancy, abundance – persistence). Patterns in mire-pool diatom communities were generally similar to those in larger organisms, and did not differ with respect to geographical range size (endemics vs. non-endemics), except at the scale of single pools. At this scale, endemic taxa, in particular E. cf. oberonica, can persist as dominant species. All the community analyses were underpinned by detailed taxonomic studies, from which I assessed over 40% of the more common species in the pools to be either endemic or likely to be endemic. Two species occurring in the study area are formally described as new species. Overall, this work highlights the vulnerability of this hidden component of New Zealand’s biodiversity to disturbances and environmental changes.

Thesis (Ph.D. ) -- McMaster University, 1999. / Includes bibliographical references [p.47-55]. Also available via World Wide Web.

Thesis (Ph.D.) - Carleton University, 2002. / Includes bibliographical references (p. 188-198). Also available in electronic format on the Internet.

Thesis (Ph.D.) - Carleton University, 2005. / Includes bibliographical references (p. 292-309). Also available in electronic format on the Internet.

Thesis (M.S.)----University of North Carolina Wilmington, 2008. / Title from PDF title page (viewed May 26, 2009) Includes bibliographical references (p. 61)

Mémoire (M.Sc.T.)--Université du Québec à Chicoutimi, 1996. / Document électronique également accessible en format PDF. CaQCU

Thesis (Ph. D.)--University of California, Riverside, 2009. / Includes abstract. Includes bibliographical references (leaves 96-102). Issued in print and online. Available via ProQuest Digital Dissertations.