Contrasting carbonate depositional systems for Pliocene cool-water limestones cropping out in central Hawke's Bay, New Zealand

Pliocene limestone formations in central Hawke's Bay (eastern North Island, New Zealand) accumulated on and near the margins of a narrow forearc basin seaway within the convergent Australia/Pacific plate boundary zone. The active tectonic setting and varied paleogeographic features of the limestone units investigated, in association with probable glacioeustatic sea-level fluctuations, resulted in complex stratigraphic architectures and contrasting types of carbonate accumulation on either side of the seaway. Here, we recognise recurring patterns of sedimentary facies, and sequences and systems tracts bounded by key physical surfaces within the limestone sheets. The facies types range from Bioclastic (B) to Siliciclastic (S) end-members via Mixed (M) carbonate-siliciclastic deposits. Skeletal components are typical cool-water associations dominated by epifaunal calcitic bivalves, bryozoans, and especially barnacles. Siliciclastic contents vary from one formation to another, and highlight siliciclastic-rich limestone units in the western ranges versus siliciclastic-poor limestone units in the eastern coastal hills. Heterogeneities in facies types, stratal patterns, and also in diagenetic pathways between eastern and western limestone units are considered to originate in the coeval occurrence in different parts of the forearc basin of two main morphodynamic carbonate systems over time

Formation of uranium disulfide from a uranium thioamidate single-source precursor

A single-source-precursor approach was developed to synthesize uranium-based materials outside of the typically-studied oxides. This approach allows for shorter reaction times, milder reaction conditions, and control over the chemicals present in synthesis. To this end, the first homoleptic uranium thioamidate complex was synthesized as a precursor for US2 materials. Pyrolysis of the thioamidate results in decomposition via an alkene elimination pathway and formation of γ-US2, which has historically been hard to access without the need for a secondary sulfur source. Despite the oxophilicity of uranium, the method successfully forms US2 without the inclusion of oxygen in the bulk final product. These findings are supported by simultaneous thermal analysis, elemental analysis, powder X-ray diffraction, and uranium L3-edge X-ray absorption fine-structure spectroscopy. This work represents the first example of a single-source precursor approach to target and synthesize actinide materials other than the oxides

Pliocene Te Aute limestones, New Zealand: Expanding concepts for cool-water shelf carbonates

Acceptance of a spectrum of warm- through cold-water shallow-marine carbonate facies has become of fundamental importance for correctly interpreting the origin and significance of all ancient platform limestones. Among other attributes, properties that have become a hallmark for characterising many Cenozoic non-tropical occurrences include: (1) the presence of common bryozoan and epifaunal bivalve skeletons; (2) a calcite-dominated mineralogy; (3) relatively thin deposits exhibiting low rates of sediment accumulation; (4) an overall destructive early diagenetic regime; and (5) that major porosity destruction and lithification occur mainly in response to chemical compaction of calcitic skeletons during moderate to deep burial. The Pliocene Te Aute limestones are non-tropical skeletal carbonates formed at paleolatitudes near 40-42°S under the influence of commonly strong tidal flows along the margins of an actively deforming and differentially uplifting forearc basin seaway, immediately inboard of the convergent Pacific-Australian plate boundary off eastern North Island, New Zealand. This dynamic depositional and tectonic setting strongly influenced both the style and subsequent diagenetic evolution of the limestones. Some of the Te Aute limestones exhibit the above kinds of "normal" non-tropical characteristics, but others do not. For example, many are barnacle and/or bivalve dominated, and several include attributes that at least superficially resemble properties of certain tropical carbonates. In this regard, a number of the limestones are infaunal bivalve rich and dominated by an aragonite over a calcite primary mineralogy, with consequently relatively high diagenetic potential. Individual limestone units are also often rather thick (e.g., up to 50-300 m), with accumulation rates from 0.2 to 0.5 m/ka, and locally as high as 1 m/ka. Moreover, there can be a remarkable array of diagenetic features in the limestones, involving grain alteration and/or cementation to widely varying extents within any, or some combination of, the marine phreatic, burial, and meteoric diagenetic environments, including locally widespread development of meteoric cement sourced from aragonite dissolution. The message is that non-tropical shelf carbonates include a more diverse array of geological settings, of skeletal and mineralogical facies, and of diagenetic features than current sedimentary models mainly advocate. While several attributes positively distinguish tropical from non-tropical limestones, continued detailed documentation of the wide spectrum of shallow-marine carbonate deposits formed outside tropical regions remains an important challenge in carbonate sedimentology

Humic Substances Enhance Chlorothalonil Phototransformation via Photoreduction and Energy Transfer

ABSTRACT: The photodegradation of chlorothalonil, a polychlorinated aromatic fungicide widely used in agriculture, was investigated under ultraviolet–visible irradiation in the presence and absence of different humic substances that significantly enhance the chlorothalonil phototransformation. On the basis of a kinetic model, an analytical study, the effect of scavengers, the chlorothalonil phosphorescence measurement, and varying irradiation conditions, it was possible to demonstrate that this accelerating effect is due to their capacity to reduce the chlorothalonil triplet state via H-donor reaction and to energy transfer from the triplet humic to ground state chlorothalonil. Energy transfer occurs at wavelengths below 450 nm and accounts for up to 30% of the reaction in deoxygenated medium upon irradiation with polychromatic light (300–450 nm). This process is more important with Elliott humic and fulvic acids and with humic acids extracted from natural carbonaceous material than with Nordic NOM and Pahokee peat humic acids. The obtained results are of high relevance to understanding the processes involved in chlorothalonil phototransformation and the photoreactivity of humic substances. Chlorothalonil is one of the rare molecules shown to react by energy transfer from excited humic substances

Sorption and Photodegradation Processes Govern Distribution and Fate of Sulfamethazine in Freshwater−Sediment Microcosms

The antibiotic sulfamethazine can be transported from manured fields to surface water bodies. We investigated the degradation and fate of sulfamethazine in pond water using 14C-phenyl-sulfamethazine in small pond water microcosms containing intact sediment and pond water. We found a 2.7-day half-life in pond water and 4.2-day half-life when sulfamethazine was added to the water (5 mg L–1 initial concentration) with swine manure diluted to simulate runoff. Sulfamethazine dissipated exponentially from the water column, with the majority of loss occurring via movement into the sediment phase. Extractable sulfamethazine in sediment accounted for 1.9–6.1% of the applied antibiotic within 14 days and then declined thereafter. Sulfamethazine was transformed mainly into nonextractable sediment-bound residue (40–60% of applied radioactivity) and smaller amounts of photoproducts. Biodegradation, as indicated by metabolite formation and 14CO2 evolution, was less significant than photodegradation. Two photoproducts accounted for 15–30% of radioactivity in the water column at the end of the 63-day study; the photoproducts were the major degradates in the aqueous and sediment phases. Other unidentified metabolites individually accounted for \u3c7% of radioactivity in the water or sediment. Less than 3% of applied radioactivity was mineralized to 14CO2. Manure input significantly increased sorption and binding of sulfamethazine residues to the sediment. These results show concurrent processes of photodegradation and sorption to sediment control aqueous concentrations and establish that sediment is a sink for sulfamethazine and sulfamethazine-related residues. Accumulation of the photoproducts and sulfamethazine in sediment may have important implications for benthic organisms

Shedding light on plant litter decomposition: Advances, implications and new directions in understanding the role of photodegradation

Litter decomposition contributes to one of the largest fluxes of carbon (C) in the terrestrial biosphere and is a primary control on nutrient cycling. The inability of models using climate and litter chemistry to predict decomposition in dry environments has stimulated investigation of non-traditional drivers of decomposition, including photodegradation, the abiotic decomposition of organic matter via exposure to solar radiation. Recent work in this developing field shows that photodegradation may substantially influence terrestrial C fluxes, including abiotic production of carbon dioxide, carbon monoxide and methane, especially in arid and semi-arid regions. Research has also produced contradictory results regarding controls on photodegradation. Here we summarize the state of knowledge about the role of photodegradation in litter decomposition and C cycling and investigate drivers of photodegradation across experiments using a meta-analysis. Overall, increasing litter exposure to solar radiation increased mass loss by 23% with large variation in photodegradation rates among and within ecosystems. This variation was tied to both litter and environmental characteristics. Photodegradation increased with litter C to nitrogen (N) ratio, but not with lignin content, suggesting that we do not yet fully understand the underlying mechanisms. Photodegradation also increased with factors that increased solar radiation exposure (latitude and litter area to mass ratio) and decreased with mean annual precipitation. The impact of photodegradation on C (and potentially N) cycling fundamentally reshapes our thinking of decomposition as a solely biological process and requires that we define the mechanisms driving photodegradation before we can accurately represent photodegradation in global C and N models. © 2012 US Government