4.6.1. The Simple Dilution Model

The principal assumption for the simple dilution model is that contaminants released into a water body uniformly mix and equilibrate with the surrounding water in an area near the effluent discharge point. This area is commonly referred to as a "mixing zone". For application of this model with dioxin-like compounds, what is desired is a concentration on the suspended solids in this mixing zone. Multiplication of the organic carbon normalized concentration on suspended solids and a Biota Suspended Solids Accumulation Factor, or BSSAF, will result in a concentration of contaminant in fish lipids. This is defined similarly to the BSAF used for other source categories of this assessment, except that the organic carbon normalized concentration is that of suspended solids rather than of bottom sediments.

The BSSAF is one of several empirical factors discussed for estimating the impact to fish in water bodies impacted by 2,3,7,8-TCDD (EPA, 1993). Others include the BSAF, total and dissolved phase bioconcentration factors (BCFs), and total and dissolved phase bioaccumulation factors (BAFs). BAFs and similar to BSAFs and BSSAFs in that all three reflect total exposure of fish to contaminant, including water column, sediment, and food chain exposures. The BCFs reflect water column exposures only. EPA (1993) states that there is currently no data available on organic carbon normalized concentrations of dioxin-like compounds on suspended solids, hence no basis to compare BSAF and BSSAF. This assessment assumes a similar numerical assignment of BSSAFs and BSAFs.

The total water concentration in a simple dilution model is:

Equation V3 4-59

Dissolved phase and suspended sediment concentrations are then estimated using an approach developed by Mills, et al. (1985) and others:

Equation V3 4-60 & 4-61

The total suspended solids concentration in the mixing zone is a function of the suspended solids just upstream of the discharge point and the suspended solids introduced in the effluent stream:

Equation V3 4-62

The suspended solids partition coefficient in the mixing zone is a function of the organic carbon partition coefficient of the contaminant and the organic carbon fraction of suspended solids:

Equation V3 4-63

This organic carbon content can be solved as the weighted average concentrations of the organic carbon contents of the suspended solids in the effluent discharge and the suspended solids of the receiving water body:

Equation V3 4-64

Fish lipid concentrations for this solution are then given as:

Equation V3 4-65

Finally, whole fish concentrations are simply this lipid concentrations times a fraction of fish lipid, or Clipid * flipid.

The key model parameter is the BSSAF. A value of 0.09 for 2,3,7,8-TCDD was assumed for BSAF based on data from Lake Ontario. One important difference between the Lake Ontario ecosystem and the effluent discharge source category is that the impact to Lake Ontario is thought to be principally historical (EPA, 1990b), while for the effluent source category, the impact is, by definition, ongoing. This difference may translate to differences in assignment of BSSAF as compared to BSAF. Consider two aquatic settings where bottom sediments are found to have equal concentrations of dioxin-like compounds - one in which contamination is ongoing and one in which contamination is primarily in the past. For the aquatic setting where contamination occurred in the past, water column and suspended sediment concentrations would be lower as compared to the aquatic setting where contamination is ongoing, because water column impacts are only a function of depuration of bottom sediments for the historically impacted water body.

It is certainly arguable that exposure of aquatic organisms is greater in the ecosystem where impacts are ongoing, as compared to a system where impacts are historical, when bottom sediment concentrations are equal in the two systems. Now recall the assumption made for the soil contamination and stack emission source categories (in both cases the water body impact is ongoing) concerning the relationship between suspended and bottom sediments - that the organic carbon normalized concentrations are equal. If this is a valid assumption for a system with ongoing impacts, and if in fact fish are relatively more exposed when impacts are ongoing rather than historical, then this argues that a BSSAF for an ongoing contamination setting should be greater in numerical value than a BSAF for a setting where contamination was historical.

However, no data could be found to support such a hypothesis, and there would be no numerical basis for an assumed difference between BSAF and BSSAF. For this reason, the values assumed for BSSAF and BSAF are equal for this assessment. It should be noted that all bioconcentration or biotransfer parameters, such as the BSSAF, are qualified as second order defaults for purposes of general use. Section 6.2. of Chapter 6 discusses the use of parameter values selected for the demonstration scenarios, including a categorization of parameters. Second order defaults are defined there as parameters which are theoretical and not site specific, but whose values are uncertain in the published literature. The parameter values in this category should be considered carefully by users of the methodology.

The effluent discharge solution algorithm was evaluated using data and information from the 104 pulp and paper mill study (EPA, 1990c), which measured discharges of 2,3,7,8-TCDD from 104 mills in 1988, and from the National Study of Chemical Residues in Fish (NSCRF; EPA, 1992a), which measured fish tissue concentrations of 2,3,7,8-TCDD at points downstream from several of these mils. A third modeling study (EPA, 1990d) collected critical data for this modeling evaluation, such as harmonic mean flows downstream of the mills. Finally, the National Council for Air and Stream Improvement (NCASI) provided details on their assessment of this data, which was used here. Importantly, this information included linking specific fish samples to specific mills. A full description of this modeling evaluation is in Chapter 7, Section

There was a dichotomy of model performance as a function of the size of the receiving water body. For most of the mills, the receiving water bodies had harmonic mean flows around 108 L/hr, with a range of 107 to 109 L/hr. A small number of mills, however, discharged into more substantial receiving water bodies which had an average flow of 5 x 1010 L/hr. Comparing model predictions of fish tissue concentrations for mills discharging into the smaller water bodies, it was found that the model tended to underpredict fish tissue concentrations - the average predicted whole fish concentration was near 7 ppt, whereas the average observed whole fish concentration was near 15 ppt. The same was not true for the large receiving water bodies. In that case, the average whole fish tissue concentration observed was an order of magnitude or more higher than predicted whole fish concentration. No precise explanation could be given for this result. The most likely explanation is that, for these large water bodies, there were other sources of dioxin releases. This comparative exercise did assume inherently that the effluent discharge was the sole source of fish tissue concentrations of 2,3,7,8-TCDD.

It was noted that, for the smaller receiving water bodies, an increase in the assumed BSSAF of 0.09 (which was the value of BSAF assumed otherwise in this assessment) to 0.20 resulted in an average model prediction of fish tissue concentration of near 15 ppt, essentially the same as the observed fish concentration. This could be some empirical evidence for the argument developed above - that the BSSAF for a system with ongoing impacts should be greater in numerical value than a BSAF developed from data on an ecosystem where impacts were primarily historical.

In any case, parameters for the demonstration scenario in Chapter 5 for this source category were derived from 104-mill data. Data from only 77 of the mills was used for the following parameter developments. Mills not included are: 1) the ten mills discharging into the largest water bodies, 2) 9 mills for which EPA (1990d) was unable to derive harmonic mean flows from STORET data, and 3) 8 mills for which data on total suspended solids content in the effluent stream was unavailable from EPA (1990c; actually 11 mills did not suspended solids data, but three were in other categories deleted).

Values of model parameters for the demonstration are now summarized:

. TSSu, TSSe:

The average upstream total suspended solids term from the 77 mills, TSSu, was 9.5 mg/L. The average suspended solids concentration within the effluent streams from the 77 mills was 70 mg/L.

. OCu, OCe:

No information was available on the organic carbon content of the suspended solids upstream of the effluent discharge point. A value of 0.05 was assigned, which was the value assigned for other source categories. No data as well could be found for the organic carbon content of the effluent solids. However, such solids are essentially biosolids from biological treatments of mill sludges. The organic carbon content of such solids is expected to be much higher than 0.05. The value recommended for OCe was 0.36 (Steven Hinton, PhD., P.E., National Council of the Paper Industry for Air and Stream Improvement, Inc.; Department of Civil Engineering, Tufts University, Medford, MA 02155). This was based on an average proportion of carbon in algal biomass of 0.36 given in Morel (1983).

. Qu, Qe:

Flow values for the receiving water and effluent stream were summarized in EPA (1990d). The average effluent flow rate, Qe, for the 77 mills was 4.10 * 106 L/hr, and for the receiving water body, Qu, was 4.65 * 108 L/hr.

. Koc, BSSAF, flipid:

Values of Koc and flipid are the same ones which have been used for the other source categories. As discussed in the introduction to this section, the Biota Suspended Solids Accumulation Factor, BSSAF, will be assumed to be the same as the Biota Sediment Accumulation, BSAF. This value is 0.09 for 2,3,7,8-TCDD.

. MASSc:

The mass of 2,3,7,8-TCDD exiting from the 77 mills averaged 0.197 mg/hr. However, this data was pertinent for 1988. Since then, pulp and paper mills have reduced the discharge of dioxin-like compounds in their effluents by altering the pulp bleaching processes. Gillespie (1992) reports that data on effluent quality from all 104 mills demonstrate reductions in discharges of 2,3,7,8-TCDD of 84%. On this basis, the value of MASSc for all three example compounds will be 0.0315 mg/hr (16% of 0.197 mg/hr).

Using these parameters in the simple dilution model for 2,3,7,8-TCDD results in the following:

1) If the mass loadings of 2,3,7,8-TCDD are assumed to be fully sorbed to solids in the effluent discharge, and not to exist in the soluble phase in the discharge, than the concentration of 2,3,7,8-TCDD on discharging effluent solids is 1.1*10-4 mg/kg, or 110 ppt.

2) The total suspended solids concentration in the mixing zone, TSSmix, equals 10.0 mg/L. The organic carbon content of suspended solids in the mixing zone, OCmix, is estimated as 0.069. It is seen how the effluent discharge influences these two key quantities: the unadjusted TSSu was given as 9.5 mg/L, and the unadjusted OCu was 0.05.

3) The overall suspended solids concentration of 2,3,7,8-TCDD in the mixing zone after mixing and equilibrating with surrounding water, Cssed, was 4.5 ppt. This compares to the concentration that might be on the effluent solids of 110 ppt, indicating more than an order of magnitude reduction in concentration by mixing with solids of the receiving water body, and partitioning into the water column.


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