Model for partitioning the non-phytoplankton absorption coefficient of seawater in the ultraviolet and visible spectral range into the contributions of non-algal particulate and dissolved organic matter.

Non-algal particles and chromophoric dissolved organic matter (CDOM) are two major classes of seawater constituents that contribute substantially to light absorption in the ocean within the ultraviolet (UV) and visible (VIS) spectral regions. The similarities in the spectral shape of these two constituent absorption coefficients, a d (λ) and a g (λ), respectively, have led to their common estimation as a single combined non-phytoplankton absorption coefficient, a d g (λ), in optical remote-sensing applications. Given the different biogeochemical and ecological roles of non-algal particles and CDOM in the ocean, it is important to determine and characterize the absorption coefficient of each of these constituents separately. We describe an ADG model that partitions a d g (λ) into a d (λ) and a g (λ). This model improves upon a recently published model [Appl. Opt.58, 3790 (2019)APOPAI0003-693510.1364/AO.58.003790] through implementation of a newly assembled dataset of hyperspectral measurements of a d (λ) and a g (λ) from diverse oceanic environments to create the spectral shape function libraries of these coefficients, a better characterization of variability in spectral shape of a d (λ) and a g (λ), and a spectral extension of model output to include the near-UV (350-400 nm) in addition to the VIS (400-700 nm) part of the spectrum. We developed and tested two variants of the ADG model: the ADG_UV-VIS model, which determines solutions over the spectral range from 350 to 700 nm, and the ADG_VIS model, which determines solutions in the VIS but can also be coupled with an independent extrapolation model to extend output to the near-UV. This specific model variant is referred to as A D G _ V I S-U V E x t . Evaluation of the model with development and independent datasets demonstrates good performance of both ADG_UV-VIS and A D G _ V I S-U V E x t . Comparative analysis of model-derived and measured values of a d (λ) and a g (λ) indicates negligible or small median bias, generally within ±5% over the majority of the 350-700 nm spectral range but extending to or above 10% near the ends of the spectrum, and the median percent difference generally below 20% with a maximum reaching about 30%. The presented ADG models are suitable for implementation as a component of algorithms in support of satellite ocean color missions, especially the NASA PACE mission.

Estimation of chromophoric dissolved organic matter and non-algal particulate absorption coefficients of seawater in the ultraviolet by extrapolation from the visible spectral region.

Extending the capabilities of optical remote sensing and inverse optical algorithms, which have been commonly focused on the visible (VIS) range of the electromagnetic spectrum, to derive the optical properties of seawater in the ultraviolet (UV) range is important to advancing the understanding of various optical, biological, and photochemical processes in the ocean. In particular, existing remote-sensing reflectance models that derive the total spectral absorption coefficient of seawater, a(λ), and absorption partitioning models that partition a(λ) into the component absorption coefficients of phytoplankton, aph(λ), non-algal (depigmented) particles, ad(λ), and chromophoric dissolved organic matter (CDOM), ag(λ), are restricted to the VIS range. We assembled a quality-controlled development dataset of hyperspectral measurements of ag(λ) (N = 1294) and ad(λ) (N = 409) spanning a wide range of values across various ocean basins, and evaluated several extrapolation methods to extend ag(λ), ad(λ), and adg(λ) ≡ ag(λ) + ad(λ) into the near-UV spectral region by examining different sections of the VIS as a basis for extrapolation, different extrapolation functions, and different spectral sampling intervals of input data in the VIS. Our analysis determined the optimal method to estimate ag(λ) and adg(λ) at near-UV wavelengths (350 to 400 nm) which relies on an exponential extrapolation of data from the 400-450 nm range. The initial ad(λ) is obtained as a difference between the extrapolated estimates of adg(λ) and ag(λ). Additional correction functions based on the analysis of differences between the extrapolated and measured values in the near-UV were defined to obtain improved final estimates of ag(λ) and ad(λ) and then the final estimates of adg(λ) as a sum of final ag(λ) and ad(λ). The extrapolation model provides very good agreement between the extrapolated and measured data in the near-UV when the input data in the blue spectral region are available at 1 or 5 nm spectral sampling intervals. There is negligible bias between the modeled and measured values of all three absorption coefficients and the median absolute percent difference (MdAPD) is small, e.g., < 5.2% for ag(λ) and < 10.5% for ad(λ) at all near-UV wavelengths when evaluated with the development dataset. Assessment of the model on an independent dataset of concurrent ag(λ) and ad(λ) measurements (N = 149) yielded similar findings with only slight reduction of performance and MdAPD remaining below 6.7% for ag(λ) and 11% for ad(λ). These results are promising for integration of the extrapolation method with absorption partitioning models operating in the VIS.

Polarized light scattering measurements as a means to characterize particle size and composition of natural assemblages of marine particles: erratum.

This erratum serves to correct an inadvertent error made during the presentation of results involving the mislabeling of the orientation of linear polarization perpendicular as parallel and vice versa in Appl. Opt.59, 8314 (2020)APOPAI0003-693510.1364/AO.396709.

Characterization of suspended particulate matter in contrasting coastal marine environments with angle-resolved polarized light scattering measurements.

Optical proxies based on light scattering measurements have potential to improve the study and monitoring of aquatic environments. In this study, we evaluated several optical proxies for characterization of particle mass concentration, composition, and size distribution of suspended particulate matter from two contrasting coastal marine environments. We expanded upon our previous study of Southern California coastal waters, which generally contained high proportions of organic particles, by conducting angle-resolved polarized light scattering measurements in predominantly turbid and inorganic-particle dominated Arctic coastal waters near Prudhoe Bay, Alaska. We observed that the particulate backscattering coefficient bbp was the most effective proxy for the mass concentration of suspended particulate matter (SPM) when compared with particulate scattering and attenuation coefficients bp and cp. Improvements were seen with bbp as a proxy for the concentration of particulate organic carbon (POC), although only if particulate assemblages were previously classified in terms of particle composition. We found that the ratio of polarized-light scattering measurements at 110º and 18º was superior in performance as a proxy for the composition parameter POC/SPM in comparison to the particulate backscattering ratio bbp/bp. The maximum value of the degree of linear polarization DoLPp,max observed within the range of scattering angles 89°-106° was found to provide a reasonably good proxy for a particle size parameter (i.e., 90th percentile of particle volume distribution) which characterizes the proportions of small- and large-sized particles. These findings can inform the development of polarized light scattering sensors to enhance the capabilities of autonomous platforms.

Polarized light scattering measurements as a means to characterize particle size and composition of natural assemblages of marine particles.

Polarized light scattering measurements have the potential to provide improved characterization of natural particle assemblages in terms of particle size and composition. However, few studies have investigated this possibility for natural assemblages of marine particles. In this study, seawater samples representing contrasting assemblages of particles from coastal environments have been comprehensively characterized with measurements of angle-resolved polarized light scattering, particle size distribution, and particle composition. We observed robust trends linking samples containing higher proportions of large-sized particles with lower values of the maximum degree of linear polarization and the second element of the scattering matrix at a scattering angle of 100°, p22(100∘). In contrast, lower values of p22(20∘) were found in more non-phytoplankton-or inorganic--dominated samples. We also determined that three measurements involving the combinations of linearly polarized incident and scattered beams at two scattering angles (110° and 18°) have the potential to serve as useful proxies for estimating particle size and composition parameters.

Polarized light scattering measurements as a means to characterize particle size and composition of natural assemblages of marine particles: publisher's note.

This publisher's note corrects an equation in Appl. Opt.59, 8314 (2020)APOPAI0003-693510.1364/AO.396709.

Optical characterization of marine phytoplankton assemblages within surface waters of the western Arctic Ocean.

An extensive data set of measurements within the Chukchi and Beaufort Seas is used to characterize the optical properties of seawater associated with different phytoplankton communities. Hierarchical cluster analysis of diagnostic pigment concentrations partitioned stations into four distinct surface phytoplankton communities based on taxonomic composition and average cell size. Concurrent optical measurements of spectral absorption and backscattering coefficients and remote-sensing reflectance were used to characterize the magnitudes and spectral shapes of seawater optical properties associated with each phytoplankton assemblage. The results demonstrate measurable differences among communities in the average spectral shapes of the phytoplankton absorption coefficient. Similar or smaller differences were also observed in the spectral shapes of nonphytoplankton absorption coefficients and the particulate backscattering coefficient. Phytoplankton on average, however, contributed only 25% or less to the total absorption coefficient of seawater. Our analyses indicate that the interplay between the magnitudes and relative contributions of all optically significant constituents generally dampens any influence of varying phytoplankton absorption spectral shapes on the total absorption coefficient, yet there is still a marked discrimination observed in the spectral shape of the ratio of the total backscattering to total absorption coefficient and remote-sensing reflectance among the phytoplankton assemblages. These spectral variations arise mainly from differences in the bio-optical environment in which specific communities were found, as opposed to differences in the spectral shapes of phytoplankton optical properties per se. These results suggest potential approaches for the development of algorithms to assess phytoplankton community composition from measurements of seawater optical properties in western Arctic waters.

Model for separating the contributions of non-algal particles and colored dissolved organic matter to light absorption by seawater.

We evaluated the performance of a recently developed absorption partitioning model [J. Geophys. Res. Oceans120, 2601 (2015)JGRCEY0148-022710.1002/2014JC010604] that derives the spectral absorption coefficients of non-algal particles, a N A P (λ), and colored dissolved organic matter, a g (λ), from the total absorption coefficient of seawater. The model's performance was found unsatisfactory when the model was tested with a large dataset of absorption measurements from diverse open-ocean and coastal aquatic environments. To address these limitations, we developed a new model based on a different approach for estimating a N A P (λ) and a g (λ) from the sum of these two coefficients, a d g (λ), within the visible spectral region. The very good overall performance of the model is demonstrated, with no tendency for bias and relatively small absolute differences (the median ≤20%) between the model-derived and measured values of a N A P (λ) and a g (λ) over a wide range of aquatic environments.

Light scattering by pure water and seawater: the depolarization ratio and its variation with salinity.

We measured the linearly polarized light scattering of pure water and seawater at various salinities and estimated the depolarization ratio using five different methods of data analysis after removing the scattering due to contamination by residual nanoparticles. The depolarization ratio values (δ) estimated for pure water using these different methods are largely consistent with each other and result in a mean value of 0.039±0.001. For seawater, our results reveal a trend of a slight linear increase of δ with salinity (S), δ=0.039+a1×S, where a1 varies in the range of 1×10-4 to 2×10-4 between the methods.

Effects of inelastic radiative processes on the determination of water-leaving spectral radiance from extrapolation of underwater near-surface measurements.

Extrapolation of near-surface underwater measurements is the most common method to estimate the water-leaving spectral radiance, Lw(λ) (where λ is the light wavelength in vacuum), and remote-sensing reflectance, Rrs(λ), for validation and vicarious calibration of satellite sensors, as well as for ocean color algorithm development. However, uncertainties in Lw(λ) arising from the extrapolation process have not been investigated in detail with regards to the potential influence of inelastic radiative processes, such as Raman scattering by water molecules and fluorescence by colored dissolved organic matter and chlorophyll-a. Using radiative transfer simulations, we examine high-depth resolution vertical profiles of the upwelling radiance, Lu(λ), and its diffuse attenuation coefficient, KLu (λ), within the top 10 m of the ocean surface layer and assess the uncertainties in extrapolated values of Lw(λ). The inelastic processes generally increase Lu and decrease KLu in the red and near-infrared (NIR) portion of the spectrum. Unlike KLu in the blue and green spectral bands, KLu in the red and NIR is strongly variable within the near-surface layer even in a perfectly homogeneous water column. The assumption of a constant KLu with depth that is typically employed in the extrapolation method can lead to significant errors in the estimate of Lw. These errors approach ∼100% at 900 nm, and the desired threshold of 5% accuracy or less cannot be achieved at wavelengths greater than 650 nm for underwater radiometric systems that typically take measurements at depths below 1 m. These errors can be reduced by measuring Lu within a much shallower surface layer of tens of centimeters thick or even less at near-infrared wavelengths longer than 800 nm, which suggests a requirement for developing appropriate radiometric instrumentation and deployment strategies.

Correction of pathlength amplification in the filter-pad technique for measurements of particulate absorption coefficient in the visible spectral region.

Spectrophotometric measurement of particulate matter retained on filters is the most common and practical method for routine determination of the spectral light absorption coefficient of aquatic particles, ap(λ), at high spectral resolution over a broad spectral range. The use of differing geometrical measurement configurations and large variations in the reported correction for pathlength amplification induced by the particle/filter matrix have hindered adoption of an established measurement protocol. We describe results of dedicated laboratory experiments with a diversity of particulate sample types to examine variation in the pathlength amplification factor for three filter measurement geometries; the filter in the transmittance configuration (T), the filter in the transmittance-reflectance configuration (T-R), and the filter placed inside an integrating sphere (IS). Relationships between optical density measured on suspensions (ODs) and filters (ODf) within the visible portion of the spectrum were evaluated for the formulation of pathlength amplification correction, with power functions providing the best functional representation of the relationship for all three geometries. Whereas the largest uncertainties occur in the T method, the IS method provided the least sample-to-sample variability and the smallest uncertainties in the relationship between ODs and ODf. For six different samples measured with 1 nm resolution within the light wavelength range from 400 to 700 nm, a median error of 7.1% is observed for predicted values of ODs using the IS method. The relationships established for the three filter-pad methods are applicable to historical and ongoing measurements; for future work, the use of the IS method is recommended whenever feasible.

Determination of the volume scattering function of aqueous particle suspensions with a laboratory multi-angle light scattering instrument.

We describe a methodology for determining the volume scattering function ß(ψ) of aqueous particle suspensions from measurements with a laboratory multi-angle light scattering instrument called DAWN (Wyatt Technology Corporation). In addition to absolute and angular calibration, the key component of the method is the algorithm correcting for reflection errors that reduce the percent error in ß(ψ) from as much as ~300% to <13% at backward scattering angles. The method is optimized and tested with simulations of three-dimensional radiative transfer of exact measurement geometry including the key components of the instrument and also validated experimentally using aqueous suspensions of polystyrene beads. Example applications of the method to samples of oceanic waters and comparisons of these measurements with results obtained with other light scattering instruments are presented.

Variability in Oceanic Particle Size Distributions and Estimation of Size Class Contributions Using a Non-parametric Approach.

A dataset of nearly 400 measurements of the particle size distribution (PSD) compiled from the Pacific, Atlantic, and Arctic Oceans is used to examine variability in the magnitude and shape of the PSD, and to characterize the partitioning of particle number, cross-sectional area, and volume concentration among defined size intervals. The results indicate that the relative contributions of three size classes based upon the pico-, nano-, and microplankton size range exhibit substantial changes among measures of particle size and between oceanic environments. The single-slope power law model commonly employed to characterize the PSD in aquatic studies is demonstrated to have significant limitations in capturing the complexity of PSD shapes observed for natural particle assemblages, and in consequence poorly predicts the relative contributions of these different size intervals. We show that specific percentile diameters derived from the cumulative distributions of particle size are strongly correlated with the contributions of these three size classes, and that these non-parametric descriptors of the cumulative distribution provide superior performance for estimating their contributions while requiring no assumption of underlying PSD shape. A comparison of these predictive relationships with independent field measurements suggests that this approach is generally robust for particle assemblages representing a wide diversity of marine environments.

Evaluation of Particle Size Distribution Metrics to Estimate the Relative Contributions of Different Size Fractions Based on Measurements in Arctic Waters.

The size distribution of suspended particles influences several processes in aquatic ecosystems, including light propagation, trophic interactions, and biogeochemical cycling. The shape of the particle size distribution (PSD) is commonly modeled as a single-slope power law in oceanographic studies, which can be used to further estimate the relative contributions of different particle size classes to particle number, area, and volume concentration. We use a data set of 168 high size-resolution PSD measurements in Arctic oceanic waters to examine variability in the shape of the PSD over the particle diameter range 0.8 to 120 µm. An average value of -3.6 ± 0.33 was obtained for the slope of a power law fitted over this size range, consistent with other studies. Our analysis indicates, however, that this model has significant limitations in adequately parameterizing the complexity of the PSD, and thus performs poorly in predicting the relative contributions of different size intervals such as those based on picoplankton, nanoplankton, and microplankton size classes. Similarly, median particle size was also generally a poor indicator of these size class contributions. Our results suggest that alternative percentile diameters derived from the cumulative distribution functions of particle number, cross-sectional area, and volume concentration may provide better metrics to capture the overall shape of the PSD and to quantify the contributions of different particle size classes.

A global compilation of in situ aquatic high spectral resolution inherent and apparent optical property data for remote sensing applications.

Light emerging from natural water bodies and measured by radiometers contains information about the local type and concentrations of phytoplankton, non-algal particles and colored dissolved organic matter in the underlying waters. An increase in spectral resolution in forthcoming satellite and airborne remote sensing missions is expected to lead to new or improved capabilities for characterizing aquatic ecosystems. Such upcoming missions include NASA's Plankton, Aerosol, Cloud, ocean Ecosystem (PACE) mission; the NASA Surface Biology and Geology designated observable mission; and NASA Airborne Visible/Infrared Imaging Spectrometer - Next Generation (AVIRIS-NG) airborne missions. In anticipation of these missions, we present an organized dataset of geographically diverse, quality-controlled, high spectral resolution inherent and apparent optical property (IOP-AOP) aquatic data. The data are intended to be of use to increase our understanding of aquatic optical properties, to develop aquatic remote sensing data product algorithms, and to perform calibration and validation activities for forthcoming aquatic-focused imaging spectrometry missions. The dataset is comprised of contributions from several investigators and investigating teams collected over a range of geographic areas and water types, including inland waters, estuaries, and oceans. Specific in situ measurements include remote-sensing reflectance, irradiance reflectance, and coefficients describing particulate absorption, particulate attenuation, non-algal particulate absorption, colored dissolved organic matter absorption, phytoplankton absorption, total absorption, total attenuation, particulate backscattering, and total backscattering. The dataset can be downloaded from https://doi.org/10.1594/PANGAEA.902230 (Casey et al., 2019).

The optical and biological properties of glacial meltwater in an Antarctic fjord.

As the Western Antarctic Peninsula (WAP) region responds to a warmer climate, the impacts of glacial meltwater on the Southern Ocean are expected to intensify. The Antarctic Peninsula fjord system offers an ideal system to understand meltwater's properties, providing an extreme in the meltwater's spatial gradient from the glacio-marine boundary to the WAP continental shelf. Glacial meltwater discharge in Arctic and Greenland fjords is typically characterized as relatively lower temperature, fresh and with high turbidity. During two cruises conducted in December 2015 and April 2016 in Andvord Bay, we found a water lens of low salinity and low temperature along the glacio-marine interface. Oxygen isotope ratios identified this water lens as a mixture of glacial ice and deep water in Gerlache Strait suggesting this is glacial meltwater. Conventional hydrographic measurements were combined with optical properties to effectively quantify its spatial extent. Fine suspended sediments associated with meltwater (nanoparticles of ~ 5nm) had a significant impact on the underwater light field and enabled the detection of meltwater characteristics and spatial distribution. In this study, we illustrate that glacial meltwater in Andvord Bay alters the inherent and apparent optical properties of the water column, and develop statistical models to predict the meltwater content from hydrographic and optical measurements. The predicted meltwater fraction is in good agreement with in-situ values. These models offer a potential for remote sensing and high-resolution detection of glacial meltwater in Antarctic waters. Furthermore, the possible influence of meltwater on phytoplankton abundance in the surface is highlighted; a significant correlation is found between meltwater fraction and chlorophyll concentration.

Treatments for paediatric femoral fractures: a randomised trial.

BACKGROUND: Treatments for femoral fractures in children vary widely and have been investigated only in case series. We did a multicentre randomised trial to compare malunion rates after external fixation and after early application of a hip spica cast for paediatric femoral shaft fractures. METHODS: All children aged 4-10 years with femoral fractures, admitted to four paediatric hospitals, were randomly assigned early application of hip spica or external fixation. The primary outcome was malunion at 2 years after the fracture. Secondary outcomes were scores on the RAND physical function child health questionnaire and the post-hospitalisation behavioural questionnaire, and parents' and children's ratings of overall satisfaction with treatment. Analysis was by intention to treat based on children who reached the 2 year evaluation. FINDINGS: Of 60 children assigned to the hip-spica group, 56 reached the 2-year assessment; of them, six (11%) required other forms of treatment because of unacceptable loss of reduction. Of 48 children assigned external fixation, 45 reached the 2-year assessment; two (4%) had refractures and five (11%) required operative adjustment of the fixator. The rate of malunion was significantly higher in the hip-spica group than in the external-fixator group (25/56 [45%] vs 7/45 [16%]; 95% CI for difference 12-46%; p=0.002). The two groups had similar mean scores for the RAND physical function health questionnaire (0.34 vs 0.45; 95% CI for difference, -0.57 to 0.34; p=0.61), for the post-hospitalisation questionnaire (106.8 vs 106.3; -4.9 to 5.9; p=0.86), and for parents' satisfaction (4.3 vs 4.2; -0.3 to 0.6; p=0.5) and children's ratings of happiness with treatment (6.9 vs 7.7; -2.2 to 0.5; p=0.21). INTERPRETATION: Early application of hip spica has a small role in the treatment of paediatric femoral fractures. Future trials need to compare external fixation with flexible intramedullary nails.

Massive phytoplankton blooms under Arctic sea ice.

Phytoplankton blooms over Arctic Ocean continental shelves are thought to be restricted to waters free of sea ice. Here, we document a massive phytoplankton bloom beneath fully consolidated pack ice far from the ice edge in the Chukchi Sea, where light transmission has increased in recent decades because of thinning ice cover and proliferation of melt ponds. The bloom was characterized by high diatom biomass and rates of growth and primary production. Evidence suggests that under-ice phytoplankton blooms may be more widespread over nutrient-rich Arctic continental shelves and that satellite-based estimates of annual primary production in these waters may be underestimated by up to 10-fold.