High-Frequency in Situ Optical Measurements During a Storm Event: Assessing Relationships Between Dissolved Organic Matter, Sediment Concentrations, and Hydrologic Processes

Dissolved organic matter (DOM) dynamics during storm events has received considerable attention in forested watersheds, but the extent to which storms impart rapid changes in DOM concentration and composition in highly disturbed agricultural watersheds remains poorly understood. In this study, we used identical in situ optical sensors for DOM fluorescence (FDOM) with and without filtration to continuously evaluate surface water DOM dynamics in a 415 km(2) agricultural watershed over a 4 week period containing a short-duration rainfall event. Peak turbidity preceded peak discharge by 4 h and increased by over 2 orders of magnitude, while the peak filtered FDOM lagged behind peak turbidity by 15 h. FDOM values reported using the filtered in situ fluorometer increased nearly fourfold and were highly correlated with dissolved organic carbon (DOC) concentrations (r(2) = 0.97), providing a highly resolved proxy for DOC throughout the study period. Discrete optical properties including specific UV absorbance (SUVA(254)), spectral slope (S(290-350)), and fluorescence index (FI) were also strongly correlated with in situ FDOM and indicate a shift toward aromatic, high molecular weight DOM from terrestrially derived sources during the storm. The lag of the peak in FDOM behind peak discharge presumably reflects the draining of watershed soils from natural and agricultural landscapes. Field and experimental evidence showed that unfiltered FDOM measurements underestimated filtered FDOM concentrations by up to similar to 60% at particle concentrations typical of many riverine systems during hydrologic events. Together, laboratory and in situ data provide insights into the timing and magnitude of changes in DOM quantity and quality during storm events in an agricultural watershed, and indicate the need for sample filtration in systems with moderate to high suspended sediment loads.

The Chemical Mechanism of a Brown-Rot Decay Mimtic System and its Application in Paper Recycling Processes

This work is aimed at improving our current knowledge of the non-enzymatic inecl~anisins involved in brown-rot decay, as well as the exploration of potential applications of a brown-rot mimetic model system in paper recycling processes. The study was divided into two parts. The first part focussed on the chemical mechanisms involved in chelation and reduction of iron by a low molecular weight chelator (isolated from the brown-rot fungus Gloeophyllz~m tmbeum) and its model compound 2,3- dihydroxybenzoic acid (2,3-DHBA). Chelation as well as free radical generation mediated by this system were studied by ESR measurement. The results indicate that the effects of the chelator/iron ratio, the pH, and other reaction parameters on hydroxyl radical generation by a Fenton type system could be determined using ESR spin-trapping techniques. The results also support the hypothesis that superoxide radicals are involved in the chelator-mediated Fenton process. In the second part of the study, the effect of a chelator-mediated Fenton system for the improvement of deinking efficiency and the n~odification of fiber and paper properties was studied. For the deinking study, copy paper was laser printed with an identical standard pattern. Then repulping and flotation operations were performed to remove ink particles. Under properly controlled deinking conditions, the chelator mediated treatment (CMT) resulted in a reduction in dirt count over that of conventional deinking procedures with no significant loss of pulp strength. To study the effect of the chelator system treatment on the quality of pulp with different fines content, a fully bleached hardwood kraft pulp was beaten to different freeness levels and treated with the chelator-mediated free radical system. The result shows that virgin fiber and heavily beaten fiber respond differently to the free radical treatment. Unbeaten fibers become more flexible and easier to collapse after free radical treatment, while beaten fibers show a reduction in fines and small materials after mild free radical treatment.

Sand geochemistry on sediment core CRP-3 from the Ross Sea, Antarctica

A total of 167 samples distubuted throughout the CRP-3 drillhole from 5.77 to 787.68 mbsf and representing fine to coarse sandstones have been analysed by X-ray fluorescence spectrometry (XRF) Bulk sample geochemistry (major and trace elements) indicates a dominant provenance of detritus from the Ferrar Supergroup in the uppermost 200 mbsf of the core. A markedly increased contribution from the Beacon sandstones is recognized below 200 mbsf and down to 600 mbsf. In the lower part of CRP-3, down to 787.68 mbsf, geochemical evidence for influxes of Ferrar materials is again recorded. On the basis of preliminary magnetostratigraphic data reported for the lower 447 mbsf of the drillhole, we tentatively evaluated the main periodicities modulating the geochemical records. Our results identify a possible influence of the precession, obliquity and long-eccentricity astronomical components (21, 41, and 400 ky frequency bands) on the deposition mechanisms of the studied glaciomarine sediments.

Investigation of Quaternary diatoms in sediment core CRP-1 from the Ross Sea, Antarctica

In the first season of drilling, the Cape Roberts Project (CRP) recovered one drillcore (CRP-l) from Roberts Ridge in western McMurdo Sound, Ross Sea, Antarctica Diatom biostratigraphy places the upper six lithostratigraphic units (Units 1.1, 2.1, 2.2, 2.3, 3.1, and 4.1) of CRP-l (0.0 to 43.15 mbsf) within the Quaternary. Both non-marine and marine Quaternary diatoms occur in variable abundance in the Quaternary interval of CRP- 1 Biostratigraphic data resolve two Quaternary time slices or events within CRP-1. Marine diatom assemblages in Units 4.1 and 3.1 represent sedimentation within the diatom Actinocyclus ingens Zone (1.35 to 0.66 Ma). Further refinement of the age of Unit 3.l places deposition in the interval 1.15 to 0.75 Ma based on the common occurrence of Thalassiosira elliptipora and correlation to the Southern Ocean acme of this taxon The absence of ActiActinocyclus ingens and the presence ot Thalassiosira antarctica in Unit 2.2 require a younger zonal assignment for this interval, within the diatom Thalassiosira lentiginosa Zone (0.66 to 0.0 Ma). A new diatom species. Rouxia leventerae, is described from marine assemblages of Units 2.2, 2.3, 3.1, and 4.l. Lithostratigraphic Unit 3.1 (33.82 to 31.89 mbsf) is a bryozoan-dominated skeletal-carbonate facies. Low abundance of Fragilariopsis curta and Fragilariopsis cylindrus within this unit combined with the relatively high abundance of species associated with open water indicates deposition in waters that remained ice free for much or all of the year Diatom assemblages suggest carbonate deposition in Unit 3.1 is linked to a significant early Pleistocene event in McMurdo Sound, when elevated surface-water temperatures inhibited the formation of sea ice.

Geochemical investigations of elements in sediment core CRP-1 from the Ross Sea, Antarctica

Geochemical data are presented for samples from strata, mainly of Miocene age, in the Cape Roberts-1 core (western McMurdo Sound, Antarctica) to assess the sediment provenance. Bulk (major and trace element) chemistry together with bulk mineralogy of fine-grained sandstones, siltstones, mudstones, and diamictites indicate that chemical alteration of source materials, fractionation due to sedimentary sorting, and diagenetic effects were not significant in the Cape Roberts sediment history. Relevant geochemical parameters are consistent with the Cape Roberts sediments being derived mainly from the crystalline basement and the Beacon Supergroup. On the basis of element distributions, an additional contribution from the Ferrar Dolerite and, mainly above about 60 m, influxes of detritus derived from basanitic to intermediate members of the McMurdo Volcanic Group are recognised.

Age determination with strontium isotopes on sediment core CRP-1 from the Ross Sea, Antarctica

Strontium isotope stratigraphy was used to date five discrete horizons within CRP-1. Early and late Quaternary (0.87-1.3 Ma and 0-0.67 Ma respectively) age sediments overlie a major sequence boundary at 43.15 meters below sea floor (mbsf). This hiatus is estimated to account for ~16 m.y. of missing section. Early Miocene (16.6-~20.8-25 Ma) age deposits below this boundary are in turn cut by multiple erosion surface representing hiatus is of between 0.2 and 1.2 m.y. Estimated minimum sedimentation rates range between 0.9 and 2.8 cm/k.y. in the Quaternary, and 1.5 and 6.4 cm/ky in the lower Miocene.

Geochemistry of bulk samples and various minerals of sediment core CRP-1 from the Ross Sea, Antarctica

Thirty-nine medium and fine grained sandstones from between 19,26 and 147,23 mbsf in the Cape Roberts-l core (CRP-1) were analysed for 10 major and 16 trace elements. Using whole-lock compositions, 9 samples were selected for analyses of mineral and glass grains by energy dispersive electron microscope. Laser-Ablation Mass-Spectrometry was used to determine rare earth elements and 14 additional trace elements in glass shards, pyroxenes and feldspars in order to examine their contribution to the bulk rock chemistry. Geochemical data reveal the major contribution played by the Granite Harbour Intrusives to the whole rock composition, even if a significant input is supplied by McMurdo volcanics and Ferrar dolerite pyroxenes McMurdo volcanics were studied in detail; they appeal to derive from a variety of litologies, and a dominant role of wind transpoitation from exposures of volcanic rocks may be inferred from the contemporary occurrence of different compositions at all depths. Only at 116.55 mbsf was a thin layer of tephra found, linked to an explosive eruption McMurdo volcanic rocks exhibit larger abundances at depths above 62 mbsf, in correspondence with the onset of volcanic activity in the McMurdo Sound area. From 62 mbsf to the bottom of the core, McMurdo volcanics are less abundant and probably issued from some centres in the McMurdo Sound region. However, available data do not allow the exclusion of wind transport from some eruptive centres active in north Victoria Land at the beginning of the Miocene Epoch.