Use of optical scattering to discriminate particle types in coastal waters

The particulate scattering characteristics of coastal waters were examined at nine locations around the United States, including near-shore sites in the Gulf of Mexico and the Atlantic and Pacific oceans. The scattering measurements were used in conjunction with inversion models to estimate particle size distributions and bulk refractive indices of the suspended particles. The relationships between various scattering properties and chlorophyll concentration were also investigated and compared with previous relationships described for case I waters. Although the general patterns of scattering and particle characteristics in coastal waters were fairly consistent, fine-scale variability within the water column was substantial. Combining optical measurements with inversion techniques provided a more informative view of the environment and a better understanding of the nature of particle populations in the coastal ocean.     

Comparison of optically derived particle size distributions: scattering over the full angular range versus diffraction at near forward angles

The volume scattering function (VSF) of particles in water depends on the particles' size distribution and composition as well as their shape and internal structure. Inversion of the VSF thus provides information about the particle population. The commercially available LISST instrument measures the scattering at near forward angles to estimate the bulk size distribution of particles larger than about 1?μm. By using scattering over the full angular range (0°-180°), the recently improved VSF-inversion method [X. Zhang, M. Twardowski, and M. Lewis, Appl. Opt. 50, 1240 (2011).10.1364/AO.50.001240APOPAI0003-6935] can characterize particles in terms of particle subpopulations, which are described by their unique size distribution and composition. Concurrent deployments of the Multispectral Volume Scattering Meter and the LISST in three coastal waters (i.e., Chesapeake Bay, Mobile Bay, and Monterey Bay) allowed us to compare the size distributions derived from these two different methods. We also obtained indirect validation of the results for submicrometer particles and for the composition of particles provided by the VSF-inversion method. For particle sizes ranging from 1 to 100?μm, the concentration was shown to vary over 10 orders of magnitude, and excellent agreement was found between the two methods with a mean relative difference less than 10% for the total size distributions. The inversion results also reproduced spectral variations in the shape of the VSF, although these spectral variations were not frequently observed in our study. The increased backscattering towards the shorter wavelengths was explained by the stronger influence of submicrometer particles affecting the backscattering. Based on published measurements of cell sizes and intracellular chlorophyll-a [Chl] concentrations over a wide range of phytoplankton species and strains, [Chl] was estimated for the inverted subpopulations that were identified as phytoplankton based on their refractive index and mean sizes. The estimated [Chl] agreed well with the fluorescence-based estimates in both magnitude and trend, thus reproducing a bloom event observed at a time series station.     

Modeling the optical properties of mineral particles suspended in seawater and their influence on ocean reflectance and chlorophyll estimation from remote sensing algorithms

The optical properties of mineral particles suspended in seawater were calculated from the Mie scattering theory for different size distributions and complex refractive indices of the particles. The ratio of the spectral backscattering coefficient to the sum of the spectral absorption and backscattering coefficients of seawater, b(b)(lambda)/[a(lambda) + b(b)(lambda)], was analyzed as a proxy for ocean reflectance for varying properties and concentrations of mineral particles. Given the plausible range of variability in the particle size distribution and the refractive index, the general parameterizations of the absorption and scattering properties of mineral particles and their effects on ocean reflectance in terms of particle mass concentration alone are inadequate. The variations in the particle size distribution and the refractive index must be taken into account. The errors in chlorophyll estimation obtained from the remote sensing algorithms that are due to the presence of mineral particles can be very large. For example, when the mineral concentration is 1 g m(-3) and the chlorophyll a concentration is low (0.05 mg m(-3)), current global algorithms based on a blue-to-green reflectance ratio can produce a chlorophyll overestimation ranging from approximately 50% to as much as 20-fold.     

Absorption and backscattering coefficients and their relations to water constituents of Poyang Lake, China

The measurement and analysis of inherent optical properties (IOPs) of the main water constituents are necessary for remote-sensing-based water quality estimation and other ecological studies of lakes. This study aimed to measure and analyze the absorption and backscattering coefficients of the main water constituents and, further, to analyze their relations to the water constituent concentrations in Poyang Lake, China. The concentrations and the absorption and backscattering coefficients of the main water constituents at 47 sampling sites were measured and analyzed as follows. (1) The concentrations of chlorophyll a (C(CHL)), dissolved organic carbon (C(DOC)), suspended particulate matter (C(SPM)), including suspended particulate inorganic matter (C(SPIM)) and suspended particulate organic matter (C(SPOM)), and the absorption coefficients of total particulate (a(p)), phytoplankton (a(ph)), nonpigment particulate (a(d)), and colored/chromophoric dissolved organic matter (a(g)) were measured in the laboratory. (2) The total backscattering coefficients, including the contribution of pure water at six wavelengths of 420, 442, 470, 510, 590, and 700 nm, were measured in the field with a HydroScat-6 backscattering sensor. (3) The backscattering coefficients without the contribution of pure water (b(b)) were then derived by subtracting the backscattering coefficients of pure water from the total backscattering coefficients. (4) The C(CHL), C(SPM), C(SPIM), C(SPOM), and C(DOC) of the 41 remaining water samples were statistically described and their correlations were analyzed. (5) The a(ph), a(d), a(p), a(g), and b(b) were visualized and analyzed, and their relations to C(CHL), C(SPM), C(SPIM), C(SPOM), or C(DOC) were studied. Results showed the following. (1) Poyang Lake was a suspended particulate inorganic matter dominant lake with low phytoplankton concentration. (2) One salient a(ph) absorption peak was found at 678 nm, and it explained 72% of the variation of C(CHL). (3) The a(d) and a(p) exponentially decreased with increasing wavelength, and they explained 74% of the variation of C(SPIM) and 71% variation of C(SPM), respectively, at a wavelength of 440 nm. (4) The a(g) also exponentially decreased with increasing wavelength, and it had no significant correlation to C(DOC) at a significance level of 0.05. (5) The b(b) decreased with increasing wavelength, and it had strong and positive correlations to C(SPM), C(SPIM) and C(SPOM), a strong and negative correlation to C(CHL), and no correlation to C(DOC) at a significance level of 0.05. Such results will be helpful for the understanding of the IOPs of Poyang Lake. They, however, only represented the IOPs during the sampling time period, and more measurements and analyses in different seasons need to be carried out in the future to ensure a comprehensive understanding of the IOPs of Poyang Lake.     

Modeling the inherent optical properties of the ocean based on the detailed composition of the planktonic community

We describe an approach to modeling the ocean's inherent optical properties (IOPs) that permits extensive analyses of IOPs as the detailed composition of suspended particulate matter is varied in a controlled manner. Example simulations of the IOP model, which includes 18 planktonic components covering a size range from submicrometer viruses and heterotrophic bacteria to microplanktonic species of 30-mum cell diameter, are discussed. Input data to the model include the spectral optical cross sections on a per particle basis and the particle-number concentration for each individual component. This approach represents a significant departure from traditional IOP and bio-optical models in which the composition of seawater is described in terms of a few components only or chlorophyll concentration alone. The simulations illustrate how the separation and understanding of the effects of various types of particle present within a water body can be achieved. In an example simulation representing an oligotrophic water body with a chlorophyll a concentration of 0.18 mg m(-3), the planktonic microorganisms altogether are the dominant particulate component in the process of light absorption, but their relative contribution to light scattering is smaller than that of nonliving particles. A series of simulations of water bodies with the same chlorophyll a concentration but dominated by different phytoplankton species shows that composition of the planktonic community is an important source of optical variability in the ocean.     

Model for the interpretation of hyperspectral remote-sensing reflectance

Remote-sensing reflectance is easier to interpret for the open ocean than for coastal regions because the optical signals are highly coupled to the phytoplankton (e.g., chlorophyll) concentrations. For estuarine or coastal waters, variable terrigenous colored dissolved organic matter (CDOM), suspended sediments, and bottom reflectance, all factors that do not covary with the pigment concentration, confound data interpretation. In this research, remote-sensing reflectance models are suggested for coastal waters, to which contributions that are due to bottom reflectance, CDOM fluorescence, and water Raman scattering are included. Through the use of two parameters to model the combination of the backscattering coefficient and the Q factor, excellent agreement was achieved between the measured and modeled remote-sensing reflectance for waters from the West Florida Shelf to the Mississippi River plume. These waters cover a range of chlorophyll of 0.2-40 mg/m(3) and gelbstoff absorption at 440 nm from 0.02-0.4 m(-1). Data with a spectral resolution of 10 nm or better, which is consistent with that provided by the airborne visible and infrared imaging spectrometer (AVIRIS) and spacecraft spectrometers, were used in the model evaluation.     

Optical scattering and backscattering by organic and inorganic particulates in U.S. coastal waters

We present the results of a study of optical scattering and backscattering of particulates for three coastal sites that represent a wide range of optical properties that are found in U.S. near-shore waters. The 6000 scattering and backscattering spectra collected for this study can be well approximated by a power-law function of wavelength. The power-law exponent for particulate scattering changes dramatically from site to site (and within each site) compared with particulate backscattering where all the spectra, except possibly the very clearest waters, cluster around a single wavelength power-law exponent of -0.94. The particulate backscattering-to-scattering ratio (the backscattering ratio) displays a wide range in wavelength dependence. This result is not consistent with scattering models that describe the bulk composition of water as a uniform mix of homogeneous spherical particles with a Junge-like power-law distribution over all particle sizes. Simultaneous particulate organic matter (POM) and particulate inorganic matter (PIM) measurements are available for some of our optical measurements, and site-averaged POM and PIM mass-specific cross sections for scattering and backscattering can be derived. Cross sections for organic and inorganic material differ at each site, and the relative contribution of organic and inorganic material to scattering and backscattering depends differently at each site on the relative amount of material that is present.     

Factor analysis of multispectral radiances over coastal and open ocean water based on radiative transfer calculations

Factor analysis is applied to multispectral (seventeen wavelengths) radiances simulated by a radiative transfer model (matrix-operator method) in and above coastal and open ocean waters. The calculated radiances were compared with measured radiances before applying factor analysis. They agree well for different sun elevations and even for turbid coastal waters. The factor analysis technique allows us to extract the characteristic signatures of phytoplankton, suspended matter, and yellow substance. The fluorescence of chlorophyll at lambda = 685 nm is found to be a clear signal for phytoplankton, also in the presence of other suspensions and yellow substance. A comparison of different algorithms for the extraction of the fluorescence peak favors the addition of chlorophyll absorption at lambda = 670 nm. The blue-green ratio is found to be useless for chlorophyll detection in coastal waters. Suspended matter and yellow substance can also clearly be seen in the factor loading for all multispectral radiances analyzed. However, suspended matter is reflected more strongly than yellow substance.     

Remote-sensing reflectance in the Beaufort and Chukchi seas: observations and models

Two semianalytical remote-sensing reflectance models were evaluated and validated by use of bio-optical data collected in the Beaufort and Chukchi seas. Both models were efficient at retrieving chlorophyll concentration, phytoplankton absorption coefficients,and particulate backscattering coefficients. In contrast, they were not accurate in predicting an absorption coefficient for colored dissolved organic matter plus nonpigmented particulates. The poor model performance is attributed to the high variability in the concentrations of these colored materials. A chlorophyll-dependent reflectance model was also assessed, and it proved to be highly successful in reproducing measured reflectance spetra. A four-component, case 2 model with mean absorption spectra for phytoplankton, soluble materials, and nonpigmented particulates was employed in Hydrolight radiative-transfer model simulations. The remote sensing reflectance spectra simulated inthe radiative-transfer model were in excellent agreement with field data. The similarity between the model and the measurement confirms the accuracy of the underlying bio-optical relationships and underscores the utility of modeling for better understanding of the variability of ocean color observations. The latest SeaWiFS algorithm (OC4V4) overestimated chlorophyll by approximately 1.5 fold across most of the observed range of biomass (0.07-9 mg chlorophyll m(-3)). Regionally tuned algorithms explained > 93% of the variability in the surface chlorophyll concentration.     

Optical closure in a complex coastal environment: particle effects

An optical dataset was collected on a mooring in the Santa Barbara Channel. Radiative transfer modeling and statistical analyses were employed to investigate sources of variability of in situ remote sensing reflectance [r(rs)(lambda,4 m)] and the f/Q ratio. It was found that the variability of inherent optical properties and the slope of the particle size distribution (xi) were strongly related to the variability of r(rs)(lambda,4 m). The variability of f/Q was strongly affected by particle type characteristics. A semianalytical radiative transfer model was applied and effects of variable particle characteristics on optical closure were evaluated. Closure was best achieved in waters composed of a mixture of biogenic and minerogenic particles.     

Effect of suspended particulate-size distribution on the backscattering ratio in the remote sensing of seawater

Mie theory is used to study the influence of the particle-size distribution (PSD) on the backscattering ratio for case 1 and 2 waters. Several in situ measured PSDs from coastal water and the open ocean, representing typical case 2 and 1 waters, were used in this investigation. Calculation of the backscattering ratio requires integration of the PSD over a much broader size range than is usually measured. Consequently extrapolation from fitted data is necessary. To that purpose the measured data are fitted with hyperbolic (Junge) and the two-component model of the PSD. It is shown that the result of extrapolation, hence the backscattering ratio, critically depends on the chosen PSD model. For a particular PSD model the role of submicrometer particles and the applied integration limits on the backscattering ratio is discussed. The use of the hyperbolic PSD model largely overestimates the number of small (submicrometer) particles that significantly contribute to backscattering and consequently leads to an erroneously high backscattering ratio. The two-component model proves to be an adequate PSD model for use in backscattering/scattering calculations providing satisfactory results complying with experimental data. The results are relevant for the inversion of remotely sensed data and the prediction of optical properties and the concentration of phytoplankton pigments, suspended sediment, and yellow substance.     

Potential impacts of nonalgal materials on water-leaving Sun induced chlorophyll fluorescence signals in coastal waters

It has been suggested that Sun induced chlorophyll fluorescence (SICF) signals could be used to estimate phytoplankton chlorophyll concentration and to investigate algal physiology from space. However, water-leaving SICF is also a product of the ambient light field. In coastal waters both algal and nonalgal materials affect the underwater light field. In this study we examine the independent impacts of varying loads of mineral suspended solids (MSS) and colored dissolved organic materials (CDOM) on water-leaving SICF signals using Hydrolight radiative transfer simulations. We show that SICF signals in coastal waters are strongly influenced by nonalgal materials. Increasing concentrations of CDOM and minerals can reduce the water-leaving SICF per unit chlorophyll by over 50% for the concentration ranges explored here (CDOM = 0 to 1 m(-1) at 440 nm, MSS=0 to 10 g m(-3)). The moderate-resolution imaging spectroradiometer (MODIS) fluorescence line height algorithm is shown to be relatively unaffected by increasing CDOM, but performance is significantly degraded by mineral concentrations greater than 5 g m(-3) owing to increased background radiance levels. The combination of these two effects means that caution is required for the interpretation of SICF signals from coastal waters.     

Local algorithms using SeaWiFS data for the retrieval of phytoplankton, pigments, suspended sediment, and yellow substance in coastal waters

Algorithms that use the SeaWiFS radiometer band reflectance data for the retrieval of phytoplankton pigment concentration, suspended sediment concentration, and yellow substance absorption in coastal water are set up by a computation based on a three-component model of sea color. The varying coastal environment is characterized by a site-specific correlation among the three parameters, subjected to large spatial and temporal fluctuations. The computation is performed with respect to the summer situation of the Gulf of Naples (Mediterranean Sea). The sensitivity of the retrieval of each parameter to variations in the concentration of the two other quantities is investigated by numerical simulations. The sensitivity to the variability of the absorption and scattering properties of phytoplankton and suspended sediment is analyzed, as well as the error induced by the uncertainty of the remote-sensing data. The algorithms's performance is satisfactorily tested on sets of SeaWiFS band reflectances randomly generated within wide water composition ranges. Although the results obtained cannot be generalized and require experimental validation, the series of tests performed suggests that the proposed algorithms, with numerical constants adjusted to the local conditions, can be effectively applied to several types of coastal environment.     

Mass-specific scattering coefficient for natural minerogenic particle populations: particle size distribution effect and closure analyses

The relationship between the particulate scattering coefficient (b(p)) and the concentration of suspended particulate matter (SPM), as represented by the mass-specific scattering coefficient of particulates (b(p)*=b(p)/SPM), depends on particle size distribution (PSD). This dependence is quantified for minerogenic particle populations in this paper through calculations of b(p)* for common minerals as idealized populations (monodispersed spheres); contemporaneous measurements of b(p), SPM, and light-scattering attributes of mineral particles with scanning electron microscopy interfaced with automated image and x-ray analyses (SAX), for a connected stream-reservoir system where minerogenic particles dominate b(p); and estimates of b(p) and its size dependency (through SAX results-driven Mie theory calculations), particle volume concentration, and b(p)*. Modest changes in minerogenic PSDs are shown to result in substantial variations in b(p)*. Good closure of the SAX-based estimates of b(p) and particle volume concentration with bulk measurements is demonstrated. Converging relationships between b(p)* and particle size, developed from three approaches, were well described by power law expressions.     

Flow cytometric determination of size and complex refractive index for marine particles: comparison with independent and bulk estimates

We advance a method to determine the diameter D and the complex refractive index (n + n'i) of marine particles from flow cytometric measurements of forward scattering, side scattering, and chlorophyll fluorescence combined with Mie theory. To understand better the application of Mie theory with its assumptions to flow cytometry (FCM) measurements of phytoplankton cells, we evaluate our flow cytometric-Mie (FCM-Mie) method by comparing results from a variety of phytoplankton cultures with independent estimates of cell D and with estimates of n and n' from the inversion of bulk measurements. Cell D initially estimated from the FCM-Mie method is lower than independent estimates, and n and n' are generally higher than bulk estimates. These differences reflect lower forward scattering and higher side scattering for single-cell measurements than predicted by Mie theory. The application of empirical scattering corrections improves FCM-Mie estimates of cell size, n, and n'; notably size is determined accurately for cells grown in both high- and low-light conditions, and n' is correlated with intracellular chlorophyll concentration. A comparison of results for phytoplankton and mineral particles suggests that differences in n between these particle types can be determined from FCM measurements. In application to natural mixtures of particles, eukaryotic pico/nanophytoplankton and Synechococcus have minimum mean values of n' in surface waters, and nonphytoplankton particles have higher values of n than phytoplankton at all depths.     

Effect of suspended particulate and dissolved organic matter on remote sensing of coastal and riverine waters

We use remote sensing reflectance (RSR) together with the inherent optical properties of suspended particulates to determine the backscattering ratio b(b)/b for coastal waters. We examine the wavelength dependence of b(b)(lambda) and f(lambda)/Q(lambda) and establish the conditions when C(lambda) in RSR(lambda) approximately or = C(lambda)b(b)(lambda)/a(lambda) can be treated as a constant. We found that for case 2 waters, RSR was insensitive to the natural fluctuations in particle-size distributions. The cross-sectional area of the suspended particulate per unit volume, x(g), showed an excellent correlation with the volume scattering coefficient.     

Remote-sensing reflectance determinations in the coastal ocean environment: impact of instrumental characteristics and environmental variability

Three independent ocean color sampling methodologies are compared to assess the potential impact of instrumental characteristics and environmental variability on shipboard remote-sensing reflectance observations from the Santa Barbara Channel, California. Results indicate that under typical field conditions, simultaneous determinations of incident irradiance can vary by 9-18%, upwelling radiance just above the sea surface by 8-18%, and remote-sensing reflectance by 12-24%. Variations in radiometric determinations can be attributed to a variety of environmental factors such as Sun angle, cloud cover, wind speed, and viewing geometry; however, wind speed is isolated as the major source of uncertainty. The above-water approach to estimating water-leaving radiance and remote-sensing reflectance is highly influenced by environmental factors. A model of the role of wind on the reflected sky radiance measured by an above-water sensor illustrates that, for clear-sky conditions and wind speeds greater than 5 m/s, determinations of water-leaving radiance at 490 nm are undercorrected by as much as 60%. A data merging procedure is presented to provide sky radiance correction parameters for above-water remote-sensing reflectance estimates. The merging results are consistent with statistical and model findings and highlight the importance of multiple field measurements in developing quality coastal oceanographic data sets for satellite ocean color algorithm development and validation.     

Bio-optical properties and ocean color algorithms for coastal waters influenced by the Mississippi River during a cold front

During the passage of a cold front in March 2002, bio-optical properties examined in coastal waters impacted by the Mississippi River indicated that westward advective flows and increasing river discharge containing high concentrations of nonalgal particles contributed significantly to surface optical variability. A comparison of seasonal data from three cruises indicated spectral models of absorption and scattering to be generally consistent with other coastal environments, while their parameterization in terms of chlorophyll (Chl) alpha concentration showed seasonal variability. The exponential slope of the colored dissolved organic matter (CDOM) averaged 0.0161+/-0.00054 nm(-1) and nonalgal absorption averaged 0.011 nm(-1) with deviations from general trends observed due to anomalous water properties. Although the phytoplankton specific absorption coefficients varied over a wide range [0.02 to 0.1 m2 (mg Chl)(-1) at 443 nm] being higher in offshore surface waters, values of phytoplankton absorption spectra at the Sea-Viewing Wide Field-of-View Sensor (SeaWiFS) wave bands were highly correlated to modeled values. Particulate scattering characteristics were similar to observations for other coastal waters, while backscattering ratios were on average lower in phytoplankton-dominated surface waters (0.011+/-0.003) and higher in low Chl near-bottom waters (0.0191+/-0.0045). Average percent differences in remote sensing reflectance Rrs derived from modeled and in-water radiometric measurements were highest in the blue wave bands (52%) and at locations with more stratified water columns. SeaWiFS estimates of Chl and CDOM absorption derived using regional empirical algorithms were highly correlated to in situ data.     

Occurrence and phase distribution of selected pharmaceuticals in the Yangtze Estuary and its coastal zone

The occurrence and geochemical behavior of nine pharmaceutical compounds were investigated along the Yangtze River Estuary and its coastal area, by sampling and analysis of pharmaceuticals in sediment, suspended particulate matter (SPM), colloidal and soluble phases. In addition, the impact of sewage input was examined by sampling from sewage treatment plants (STP) effluent and its upstream and downstream in the Yangtze River. Although at relatively low concentrations in SPM and sediments, several pharmaceuticals were found at elevated concentration in filtered water samples from STP-affected sites. STP is therefore an important input of pharmaceuticals in the study area. Colloidal phase was further separated from bulk water samples using cross-flow ultrafiltration (CFUF), confirming it being an effective sorbent for pharmaceuticals with high sorption capacity which are 2-4 orders of magnitude higher than SPM. Moreover, mass balance calculations showed that significant percentages of selected pharmaceutical compounds were associated with aquatic colloids, indicating colloids as a reservoir for these contaminants in the Yangtze estuarine system.     

Retrieval of chlorophyll from remote-sensing reflectance in the china seas

The East China Sea is a typical case 2 water environment, where concentrations of phytoplankton pigments, suspended matter, and chromophoric dissolved organic matter (CDOM) are all higher than those in the open oceans, because of the discharge from the Yangtze River and the Yellow River. By using a hyperspectral semianalytical model, we simulated a set of remote-sensing reflectance for a variety of chlorophyll, suspended matter, and CDOM concentrations. From this simulated data set, a new algorithm for the retrieval of chlorophyll concentration from remote-sensing reflectance is proposed. For this method, we took into account the 682-nm spectral channel in addition to the Sea-viewing Wide Field-of-view Sensor (SeaWiFS) channels. When this algorithm was applied to a field data set, the chlorophyll concentrations retrieved through the new algorithm were consistent with field measurements to within a small error of 18%, in contrast with that of 147% between the SeaWiFS ocean chlorophyll 2 algorithm and the in situ observation.