Chromatographic studies of dissolved organic matter and copper-organic complexes isolated from estuarine waters

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography (RPLC). Different types of reverse-phase BOND ELUT columns (Analytichem International), including C₂, C₁₈ and phenyl-bonded phases, were studied to determine their adsorption efficiency for extracting DOM. Extraction efficiencies followed the order phenyl > C₁₈ > C₂, and phenyl − C₁₈ > C₂ for DOM and organic copper, respectively. However, comparisons of BOND ELUT and C₁₈ SEP-PAK (Waters Associates) columns indicated that SEP-PAK columns were the most efficient when both DOM and organic copper were considered. Chromatographic profiles of the isolated DOM obtained using high-performance liquid chromatography were similar in elution characteristics and resembled chromatograms typical of fulvic acid. The UV-absorption characteristics of the DOM showed small differences and suggested that the different reverse-phase columns isolated material that was qualitatively similar.Copper-organic complexes isolated using C₁₈ RPLC were studied to examine the dissociation of organically bound copper in seawater as the pH is lowered. Only a small amount of the complexed copper was displaced by the H⁺ with about 40% of the copper remaining bound at pH 3. However, the chromatographic elution behavior of the DOM and organic copper was significantly altered under acidic conditions as a result of protonation of acidic functional sites on the organic matter.     

Demystifying Fisher Information: What Observation Data Reveal about Our Models

Information theory is the basis for understanding how information is transmitted as observations. Observation data can be used to compare uncertainty on parameter estimates and predictions between models. Jacobian Information (JI) is quantified as the determinant of the weighted Jacobian (sensitivity) matrix. Fisher Information (FI) is quantified as the determinant of the weighted FI matrix. FI measures the relative disorder of a model (entropy) in a set of models. One‐dimensional models are used to demonstrate the relationship between JI and FI, and the resulting uncertainty on estimated parameter values and model predictions for increasing model complexity, different model structures, different boundary conditions, and over‐fitted models. Greater model complexity results in increased JI accompanied by an increase in parameter and prediction uncertainty. FI generally increases with increasing model complexity unless model error is large. Models with lower FI have a higher level of disorder (increase in entropy) which results in greater uncertainty of parameter estimates and model predictions. A constant‐head boundary constrains the heads in the area near the boundary, reducing sensitivity of simulated equivalents to estimated parameters. JI and FI are lower for this boundary condition as compared to a constant‐outflow boundary in which the heads in the area of the boundary can adjust freely. Complex, over‐fitted models, in which the structure of the model is not supported by the observation dataset, result in lower JI and FI because there is insufficient information to estimate all parameters in the model.     

Reviewing the Yarkovsky effect: New light on the delivery of stone and iron meteorites from the asteroid belt

Abstract— We give a nonmathematical review of recent work regarding the Yarkovsky effect on asteroidal fragments. This effect may play a critical, but underappreciated, role in delivering meteorites to Earth. Two variants of the effect cause drifts in orbital elements, notably semimajor axes. The “classic” or “diurnal” Yarkovsky effect is associated with diurnal rotation at low obliquity. More recently, a “seasonal” effect has also been described, associated with high obliquity. Studies of these Yarkovsky effects are combined with studies of resonance effects to clarify meteorite delivery. If there were no Yarkovsky drift, asteroid fragments could reach a resonance only if produced very near that resonance. However, objects in resonances typically reach Earth-crossing orbits within a few million years, which is inconsistent with stone meteorites' cosmic-ray exposure (CRE) ages (5–50 Ma) and iron meteorites' CRE ages (100–1000 Ma). In the new view, on the other hand, large objects in the asteroid belt are “fixed” in semimajor axis, but bodies up to 100 m in diameter are in a constant state of mixing and flow, especially if the thermal conductivity of their surface layers is low. Thus, small asteroid fragments may reach the resonances after long periods of drift in the main belt. Yarkovsky drift effects, combined with resonance effects, appear to explain many meteorite properties, including: (1) the long CRE ages of iron meteorites (due to extensive drift lifetimes in the belt); (2) iron meteorites' sampling of numerous parent bodies; (3) the shorter CRE ages of most stone meteorites (due to faster drift, coupled with weaker strength and more rapid collisional erosion); and (4) the abundance of falls from discrete impact events near resonances, such as the 8 Ma CRE age of H chondrites. Other consequences include: the delivery of meteorite parent bodies to resonances is enhanced; proportions of stone and iron meteorites delivered to Earth may be different from the proportions at the same sizes left in the belt, which in turn may differ from the ratio produced in asteroidal collisions; Rabinowitz's 10–100 m objects may be preferentially delivered to near-Earth space; and the delivery of C-class fragments from the outer belt may be inhibited, compared to classes in other parts of the belt. Thus, Yarkovsky effects may have important consequences in meteoritics and asteroid science.     

Multiproxy Analyses of Stratigraphy and Palaeoenvironment of the Late Palaeolithic Grabow Floodplain Site,Northern Germany

Changing river courses and fluctuations of the water table were some of the most fundamental environmental changes that humans faced during the Late Glacial, particularly as these changes affected areas intensively used for settlement and resource exploitation. Unfortunately, only a few stratigraphies have been documented in the North European plain that show the interaction between river development, vegetation history, and occupation by Late Palaeolithic humans. Here, we present the results of detailed stratigraphical studies (pedology, archaeology, chrono‐, tephra‐, and palynostratigraphy) at the Federmesser site Grabow 15 located in the broad Elbe River valley. The research aimed to produce a model of site formation based on a multiproxy approach, relating the local evidence to the palaeoenvironmental and settlement history of the wider region. After deposition of fluvial sands during the Late Pleniglacial in a braided setting, the river course developed locally toward a meandering system at the transition from the Older Dryas to the Allerød, while periodic flooding led to the deposition of floodplain sediments during the early Allerød. The floodplain was settled by people of the earliest “Federmessergruppen,” who are believed to have chosen this open floodplain area along the river for collecting and processing amber of local origin. Their artifacts became embedded in the aggrading floodplain sediments. In the late Allerød, floodplain sedimentation ceased and a Fluvisol‐type soil developed, indicating a trend toward geomorphic stability. The Fluvisol was then covered by silty floodplain sediments due to a rising water level during the late Younger Dryas resulting in the cessation of human occupation in the area. Subsequent organic‐rich Late Glacial/Holocene sediments preserved the settlement remains to the present.     

Developing carbon budgets for UK agriculture, land-use, land-use change and forestry out to 2022

This paper derives a notional future carbon budget for UK agriculture, land use, land use change and forestry sectors (ALULUCF). The budget is based on a bottom-up marginal abatement cost curve (MACC) derived for a range of mitigation measures for specified adoption scenarios for the years 2012, 2017 and 2022. The results indicate that in 2022 around 6.36 MtCO₂e could be abated at negative or zero cost. Furthermore, in the same year, over 17% of agricultural GHG emissions (7.85 MtCO₂e) could be abated at a cost of less than the 2022 Shadow Price of Carbon (£34 (tCO₂e)^???1). The development of robust MACCs faces a range of methodological hurdles that complicate cost-effectiveness appraisal in ALULUCF relative to other sectors. Nevertheless, the current analysis provides an initial route map of efficient measures for mitigation in UK agriculture.