Commonly Used Models for IOPs and Biogeochemistry
Commonly Used Models relating IOPs and underlying biogeochemistry
Models IOPs and AOPs are analytical expressions relating them to bio-geochemical parameters (e.g. Chlorophyll, Suspended Matter) and/or describe their spectrum (relating their value at one wavelength with their value at another wavelength). Below is a ”laundry list” of such models we assembled from the literature (see also Sosik (2008) for a recent compilation). This list is not exhaustive and we invite the readers to point our to us useful models they have developed or know oﬀ that we have not included. The user of such models are cautioned that they were designed with a speciﬁc data sets and a speciﬁc application in mind which may or not be applicable to the conditions the user is applying it to. Also, it is important to note that the ﬁt parameters will vary depending on the way a model is ﬁt to the data (e.g. how uncertainties are assumed to behave) and the spectral range that is ﬁt (e.g. Twardowski et al. (2004). Note that some of the observed variability in relationships is likely due to methodology in biogeochemical determinations (e.g. ﬁltration), may be due to instrumental issues (e.g. spectral ﬁlters used (narrow vs. wide) and acceptance angle (e.g. Boss et al. (2009)). In addition, empirical relationships are likely to be biased to time and location of data used to derive them, and their generalization should be done with caution.
CDOM spectrum is the visible is most often described by an exponentially decreasing function:
where is referred to as the spectral slope and a reference wavelength. A theoretical explanation for this shape has been hypothesized by Shifrin (1988) as arising from a superposition of resonances of diﬀerent molecular -bonds in the long organic molecules comprising CDOM. Single bonds, which are most abundant, will absorb short wavelength radiation while resonance of multiple bond, less abundant, absorb longer wavelength radiation. This explanation is consistent with the observation that small values of the spectral slope of CDOM, , are associated with higher molecular weight materials (e.g. Carder et al. (1989), Yacobi et al. (2003)). For visible wavelength the most common values of appear to be near 0.014 , varying in the visible from 0.007 to 0.026 (e.g. Table 1 in Twardowski et al. (2004).
While this is the most frequent model of CDOM absorption, other models have been suggested that may provide better ﬁt to data (even when taking into account that ﬁts improve as more free parameters are available in the ﬁt, e.g. Twardowski et al. (2004). In particular, often a constant is added to the exponential ﬁt:
What this constant represent is not clear. In some cases it is supposed to account for scattering by the dissolved component, however there is no reason to believe such scattering would be spectrally ﬂat (see Bricaud et al. (1981) for in-depth discussion). It may account for bubbles in the sample.
Another model that has been found to work even better than the exponential model is the power-law model (e.g. Twardowski et al. (2004).
In estuaries and coastal waters CDOM and ﬂuorescence by DOM vary in correlation with DOM (e.g. Blough and Green (1995). Relationships are of the type:
for a whole variety of environmental samples as well as extracted fulvic and humic materials and where DOC has units of . When restricted to whole environmental samples (and including data from Vodacek et al. (1997)
Such relationship is not observed in open waters (Nelson and Seigel (2002)). However, the values of DOC observed in the open ocean (e.g. 48-68 , Nelson and Seigel (2002)), are of the similar magnitude as the intercept of - regressions ( 70 Vodacek et al. (1997)) and hence represent, to a large extent, the surface pool of uncolored DOC. These relationship arise from a end-member mixing between terrestrial and oceanic water masses and do not hold in coastal areas not strongly aﬀected by river inputs and where CDOM sinks (e.g. photooxydation) aﬀect CDOM concentrations signiﬁcantly Blough and DelVeccio (2002)).
Between rivers and estuaries increases with increases aromatic content and thus with lower CDOM spectral slopes (Blough and DelVeccio (2002)).
Prieur and Sathyendranath (1981) suggest the following model
Babin et al. (2003b) has also found a linear relationship between CDOM and Chl for European waters.
Similar to CDOM, the absorption of NAP is usually modeled with a decreasing exponential function (Yentsch (1962); Kirk (1980); Roesler et al. (1989); Bricaud et al. (1998)):
where is a reference wavelength and the spectral slope (independent of ). The mean slope () generally used to model is 0.011 (Roesler et al. (1989) Bricaud et al. (1998)). It should be noted that the exponential function is only an approximation and that realistic NAP spectra may be non monotonic and often exhibit a ’hump’ in the blue (e.g. Itturiaga and Siegel (19xx)).
For non-algal particles both collected in coastal and riverine waters and from mineral samples, Babin et al. (Babin et al. (2003); Babin et al. (2004)) found:
with the high values being associated with high iron-oxides content. Relationships with iron concentrations are signiﬁcantly better Babin et al. (2004):
Where is given in
where PM is in .
where PM is in .
In open ocean environments (Morel, 2008):
While in more turbid waters the leading coeﬃcient exceeds 0.45 and [Chl] is in . For the upper layer, and based on more recent measurements (Loisel and Morel (1998))
Babin et al., 2003b found that
where PM is the particulate matter concentration in . the lower values come from turbid coastal areas while the open water values are high. This relatively tight relationship was explained as arising from the relative insensitivity to particle composition (PM is the dried mass) using theoretical calculations. Boss et al. (Boss et al. (2009b)), showed that the relative insensitivity of this relationship to variability in size composition may be due to aggregation.
In open ocean environments (Morel, 2008):
is always smaller than by about 30 in absorbing bands and by more than 100 in weakly absorbing bands such as in the green pat of the spectrum.