Photobleaching of chromophoric dissolved organic matter in natural waters: kinetics and modeling

The effects of monochromatic and polychromatic UV and visible (VIS) radiation on the optical properties (absorption and fluorescence) of chromophoric dissolved organic matter (CDOM) were examined for a Suwannee River fulvic acid (SRFA) standard and for water from the Delaware and Chesapeake Bays. The primary (direct) loss of absorption and fluorescence occurred at the irradiation wavelength(s), with smaller secondary (indirect) losses occurring outside the irradiation wavelength(s). The efficiency of both direct and indirect photobleaching decreased monotonically with increasing wavelength. Exposure to polychromatic light increased the CDOM absorption spectral slope (S), consistent with previous field measurements. An analysis of the monochromatic photobleaching kinetics argues that a model based on a simple superposition of multiple chromophores undergoing independent photobleaching cannot apply; this conclusion further implies that the absorption spectrum of CDOM cannot arise solely from a simple superposition of the spectra of numerous independent chromophores. The kinetics of CDOM absorption loss with the monochromatic irradiation were employed to create a simple, heuristic model of photobleaching. This model allowed us to examine the importance of the indirect photobleaching losses in determining the overall photobleaching rates as well as to model the photobleaching of natural waters under polychromatic light fields. Application of this model to natural waters closely predicted the change in the CDOM spectral shape caused by photodegradation. The time scale of this process was consistent with field observations acquired during the summertime for coastal waters in the Middle Atlantic Bight (MAB). The results indicate that the ratio of the photodegradation depth to the mixed layer depth is a key parameter controlling the rate of the photobleaching in surface waters.     

Channelled erosion through a marine dump site of dredge spoils at the mouth of the Puyallup River, Washington State, USA

Channels are relatively common on river-mouth deltas, but the process by which they arise from river sediment discharge is unclear because they can potentially be explained either by negatively buoyant (hyperpycnal) flows produced directly from the river outflow or by flows generated by repeated failure and mobilisation of sediment rapidly deposited at the delta front. Channels eroded through a dump site of dredge spoils are described here from multibeam and older sonar data collected in Commencement Bay, at the mouth of the Puyallup River. Shallow channels on the seaward upper surface of the dump site, away from any flows that could have been produced by delta front failures, suggest that at least some hyperpycnal flows were produced directly from the positively buoyant river outflow up to 200 m from the edge of the river mouth platform. The form of channel bed erosion is revealed by the longitudinal shape of the main eroded channel compared with the adjacent dump site profile. It suggests that the channel evolved by its steep front retreating, rather than by simple vertical entrenchment or diffusive-like evolution of the profile, a geometry interpreted as evidence that repeated failure of the bed occurred in response to shear stress imposed by bottom-travelling flows. Model calculations based on shear strengths back-calculated from the geometry of channel wall failures suggest that, if the main channel were eroded solely by hyperpycnal flows, their generation was remarkably efficient in order to create flows vigorous enough to cause channel bed failure. Besides the sediment concentration and discharge characteristics that have been considered to dictate the ability of rivers to produce hyperpycnal flows, it is suggested that the timing of floods with respect to the tidal cycle should also be important because extreme low tides may be needed to ensure that coarse sediment is transferred vigorously to the edge of river mouth platforms.     

Equatorial Pacific gravity lineaments: interpretations with basement topography along seismic reflection lines

The central equatorial Pacific is interesting for studying clues to upper mantle processes, as the region lacks complicating effects of continental remnants or major volcanic plateaus. In particular, the most recently produced maps of the free-air gravity field from satellite altimetry show in greater detail the previously reported lineaments west of the East Pacific Rise (EPR) that are aligned with plate motion over the mantle and originally suggested to have formed from mantle convection rolls. In contrast, the gravity field 600 km or farther west of the EPR reveals lineaments with varied orientations. Some are also parallel with plate motion over the mantle but others are sub-parallel with fracture zones or have other orientations. This region is covered by pelagic sediments reaching ~?500–600 m thickness so bathymetry is not so useful for seeking evidence for plate deformation across the lineaments. We instead use depth to basement from three seismic reflection cruises. In some segments of these seismic data crossing the lineaments, we find that the co-variation between gravity and basement depth is roughly compatible with typical densities of basement rocks (basalt, gabbro or mantle), as expected for some explanations for the lineaments (e.g., mantle convection rolls, viscous asthenospheric inter-fingering or extensional deformation). However, some other lineaments are associated with major changes in basement depth with only subtle changes in the gravity field, suggesting topography that is locally supported by varied crustal thickness. Overall, the multiple gravity lineament orientations suggest that they have multiple origins. In particular, we propose that a further asthenospheric inter-fingering instability mechanism could occur from pressure variations in the asthenosphere arising from regional topography and such a mechanism may explain some obliquely oriented gravity lineaments that have no other obvious origin.     

Soil sorption of caesium modelled by the Langmuir and Freundlich isotherm equations

The Langmuir and Freundlich adsorption isotherm equations were used to model Cs sorption in 6 Welsh soils. The pH (in water), of the soils ranged from 3.5 to 6.5, and the estimated organic matter (determined by loss-on-ignition) ranged from 4.8% to 46%. According to the Langmuir adsorption isotherm, highest sorption maxima,b, were displayed by the loams at 102–204 mg kg⁻¹, compared with organic soils at 37–86 mg kg⁻¹. Subsoil horizons (15–30 cm depth) did not always display higher sorption maxima than their topsoil (0–15 cm depth) counterparts. Where an improved fit to the Freundlich model was found over the Langmuir model, it was assumed that either concurrent desorption of other species, or bond-energy heterogeneity in the substrate, were significant for these soils.     

Fossilisation of a silica diagenesis reaction front on the mid-Norwegian margin

The diagenetic transformation of biogenic silica from opal-A to opal-CT was recognised on seismic reflection data over an area of 78 × 10³ km² on the mid-Norwegian margin. The opal-A/CT diagenetic boundary appears as a positive, high amplitude reflection that generally cross-cuts the hosting stratigraphy. We demonstrate that it is not a sea bottom simulating reflection (BSR) and also that is not in thermal equilibrium with the present day isotherms. We present arguments that three styles of deformation associated with the opal-A/CT reflection – polygonal faulting, regional anticlines and synclines and differential compaction folding – indicate that the silica diagenesis reaction front is fossilised at a regional scale. Isochore maps demonstrate the degree of conformity between the opal-A/CT reflection and three seismic horizons of Late Miocene to Early Pliocene age that potentially represent the paleo-seabed when ‘fossilisation’ of the reaction front took place. The seismic interpretational criteria for recognition of a fossilised diagenetic front are evaluated and the results of our study are integrated with previous studies from other basins of the NE Atlantic in order to determine if the arrest of silica diagenesis was diachronous along this continental margin.     

Stakeholder consultation during the planning phase of scientific programs

Stakeholder consultation is being adopted as standard practice in the planning and management of natural resource management programs. While the utility of stakeholder participation has been investigated for the evaluation and implementation phases of natural resource management programs, few studies have examined the utility of stakeholder consultation during the initial phases of developing such programs. This paper presents a case study from a project developing a marine and coastal monitoring program for the Pilbara and Kimberley region of northern Western Australia. Via a series of workshops held in the region, stakeholders were asked to prioritise future research needs using several voting procedures. During the analyses of the results from the different voting procedures, it became apparent that there were high levels of inconsistency, poor correlation, and contradiction, between participants’ responses. Despite the rigour of the selection process used to identify ‘suitable’ stakeholders for the workshops, these results show that stakeholders did not have the technical or broader contextual knowledge about marine ecosystems to effectively and objectively contribute to the research prioritisation and planning process. Based on the outcomes of this study, we argue that project designers need to be clear about why they are involving stakeholders in a project, particularly in light of the costs involved (financial, time, resources, costs to the stakeholder) in stakeholder consultation. Stakeholder involvement may be appropriate in later stages of developing natural resource management programs (implementation and management), however, stakeholder involvement is not appropriate in the initial phases of such programs, where scientific expertise is essential in formulating scientific concepts and frameworks.     

Non-equilibrium flocculation characteristics of fine-grained sediments in grid-generated turbulent flow

Results are presented from a series of settling column experiments investigating temporal variations in the flocculation characteristics of purely cohesive (kaolin clay) sediment suspensions and cohesive (kaolin) and non-cohesive (fine sand) sediment fraction mixtures. Experimental runs were conducted under controlled hydrodynamic conditions generated by a rigid array of in-phase oscillating grids. The results indicated that rapid initial floc aggregation occurred under low turbulent shear rates, with peak maximal and root-mean-square (r.m.s.) floc sizes (∼ 400 μm and ∼ 200 μm, respectively) attained after relatively short time periods, before reducing with time. By contrast, lower aggregation rates and smaller floc sizes were observed under higher shear conditions, with flocs retaining suspended in the settling column for longer time scales due to the increased turbulence. The mud input concentration displayed some correlation with maximal and r.m.s. floc sizes at higher shear rates but no correlation was apparent at low shear rates. This observed floc behaviour may be attributed to the differences in concentration gradients at high and low shear rates that affect both floc settling rate and time required for flocs to attain equilibrium size. The addition of the fine sand fraction to the kaolin clay suspension reduced both the initial floc formation (i.e. aggregation) rate and the maximal and r.m.s. floc sizes attained throughout the experiments. The reduction in maximal floc sizes appeared to be enhanced by an increase in the ratio of fine sand to kaolin clay content within the mixture.     

A comparison of the main methods for estimating probabilities of extreme still water levels

Sea-level return periods are estimated at 18 sites around the English Channel using: (i) the annual maxima method; (ii) the r-largest method; (iii) the joint probability method; and (iv) the revised joint probability method. Tests are undertaken to determine how sensitive these four methods are to three factors which may significantly influence the results; (a) the treatment of the long-term trends in extreme sea level; (b) the relative magnitudes of the tidal and non-tidal components of sea level; and (c) the frequency, length and completeness of the available data. Results show that unless sea-level records with lengths of at least 50 years are used, the way in which the long-term trends is handled in the different methods can lead to significant differences in the estimated return levels. The direct methods (i.e. methods i and ii) underestimate the long (> 20 years) period return levels when the astronomical tidal variations of sea level (relative to a mean of zero) are about twice that of the non-tidal variations. The performance of each of the four methods is assessed using prediction errors (the difference between the return periods of the observed maximum level at each site and the corresponding data range). Finally, return periods, estimated using the four methods, are compared with estimates from the spatial revised joint probability method along the UK south coast and are found to be significantly larger at most sites along this coast, due to the comparatively short records originally used to calibrate the model in this area. The revised joint probability method is found to have the lowest prediction errors at most sites analysed and this method is recommended for application wherever possible. However, no method can compensate for poor data.     

Geochemical and oxygen isotope perspective of a new R chondrite Dhofar 1671: Affinity with ordinary chondrites

Dhofar 1671 is a relatively new meteorite that previous studies suggest belongs to the Rumuruti chondrite class. Major and REE compositions are generally in agreement with average values of the R chondrites (RCs). Moderately volatile elements such as Se and Zn abundances are lower than the R chondrite values that are similar to those in ordinary chondrites (OCs). Porphyritic olivine pyroxene (POP), radial pyroxene (RP), and barred olivine (BO) chondrules are embedded in a proportionately equal volume of matrix, one of the characteristic features of RCs. Microprobe analyses demonstrate compositional zoning in chondrule and matrix olivines showing Fa‐poor interior and Fa‐rich outer zones. Precise oxygen isotope data for chondrules and matrix obtained by laser‐assisted fluorination show a genetic isotopic relationship between OCs and RCs. On the basis of our data, we propose a strong affinity between these groups and suggest that OC chondrule precursors could have interacted with a ¹⁷O‐rich matrix to form RC chondrules (i.e., ?¹⁷O shifts from ~1‰ to ~3‰). These interactions could have occurred at the same time as “exotic” clasts in brecciated samples formed such as NWA 10214 (LL3–6), Parnallee (LL3), PCA91241 (R3.8–6), and Dhofar 1671 (R3.6). We also infer that the source of the oxidation and ¹⁷O enrichment is the matrix, which may have been enriched in ¹⁷O‐rich water. The abundance of matrix in RCs relative to OCs, ensured that these rocks would be apparently more oxidized and appreciably ¹⁷O‐enriched. In situ analysis of Dhofar 1671 is recommended to further strengthen the link between OCs and RCs.     

On the Long-Term Evolution of the Sensitivity of the STEREO HI-1 Cameras

The Heliospheric Imagers (HI) on the Solar TErrestrial RElations Observatory (STEREO) observe the solar wind and disturbances therein as it propagates from close to the Sun to 1 AU and beyond. In this article we use stellar photometry over much of the mission to date to make a determination of the long-term evolution of the photometric response of the inner (HI-1) cameras. We find very slow degradation rates of the order of 0.1 % per year, similar to those found for HI-2 by Tappin, Eyles and Davies (Solar Phys. 290, 2143, 2015) and significantly slower than rates found for other comparable instruments. We also find that it is necessary to make a small (\({\approx}\,1~\%\)) revision to the photometric calibration parameters used to convert instrument units into physical units. Finally, we briefly discuss the effects of pointing instabilities on the measurement of stellar count rates.