concentration results. Pulp and paper mills with and without chlorine were listed as point sources for 125 episodes (an episode is a fish sampling site). In 37 of these episodes, other point sources were identified, including one or more of the following: refinery (refinery using the catalytic reforming process), NPL site (a Superfund site), or other industry (an industrial discharge other than a paper mill or refinery). Given other sources, it is in fact a benefit to the exercise that predictions were lower than observations.
3. The model more closely predicts fish concentrations for the smaller receiving water bodies when the BSSAF is calibrated from 0.09 to 0.20. Considering that 0.09 was a value for 2,3,7,8-TCDD developed with data from Lake Ontario, a standing water body with principally historic and not ongoing 2,3,7,8-TCDD impacts, this setting is probably an inappropriate surrogate for ongoing discharges to a riverine situation. This would argue that a calibration is warranted.
7.2.3.7. Examination of observed air concentrations
The volatilization and near-field dispersion models of the soil source category were developed from well established theoretical principals, and were developed as part of an effort to assess the impact of soils contaminated with PCBs (Hwang, et al., 1986). The virtual point source dispersion model for far-field dispersion estimates is also based on well established theory (Turner, 1970). However, these models have not been field validated for soils contaminated with dioxin-like compounds. Ideally, the algorithms for estimating air concentrations would be validated using data on soil concentrations of dioxin-like compounds and concurrently measured concentrations in air above and downwind of the contaminated soil. A discussion of the Gaussian plume dispersion theories used in the COMPDEP model is given in Chapter 3, Section 3.4.1.
Some sense of the reasonableness of model values can be made by comparing predictions to measured concentrations in ambient air in urban environments. Reports of such concentrations are summarized in Section 4.7, Chapter 4 of Volume II, and Tables B.14-B.16, Appendix B of Volume II. Sources other than soil are likely to be the cause of levels measured in urban air environments. Also, the dispersion model is designed for situations where the contaminated soil is surrounded by relatively clean soil. As discussed in Section 7.2.3.1 above, off-site impacts have been noted in several sites of 2,3,7,8-TCDD contamination. These two points are made in order to establish a basis for comparing urban air concentration to concentrations predicted to occur from soils: one would expect urban air concentrations to be at least higher, if not higher by orders of magnitude, than soil emissions.
Tables B.14 and B.15 (Appendix B, Volume II) summarize average PCDD/PCDF congener-specific concentrations in urban air in the United States and in Europe. Results for two example compounds demonstrated in Chapter 5, 2,3,7,8-TCDD and 2,3,4,7,8-PCDF, are examined in this section. Observed concentrations of 2,3,7,8-TCDD were mostly non-detects with detection limits ranging from 0.01 to as high as 0.82 pg/m3. Occurrences were noted as high as 0.05 pg/m3 in Bridgeport, CT, and 0.004 pg/m3 in Wallingford, CT (both measurements as part of a study evaluating the impact of resource recovery facilities) and 0.06-0.08 pg/m3 in urban settings in Hamburg, Germany. In Stockholm, Sweden, occurrences in suburban, remote countryside, and coastal settings were listed at 0.0007, 0.0002, and 0.0001 pg/m3 respectively. Concentrations of 2,3,4,7,8-PCDF were detected in several reported studies. The range of 2,3,4,7,8-PCDF detections was 0.001-1.92 pg/m3. In the few reports where both compounds were detected, 2,3,4,7,8-PCDF was detected at 3 to 10 times higher concentration than 2,3,7,8-TCDD.
Eight air monitoring studies in the United States were used to arrive at a profile of air concentrations used for estimating background exposures to dioxin-like compounds through inhalation. These references were characterized as mostly urban and suburban, not background or rural. A summary of this compilation is in Volume II, Chapter 4, Section 4.7. and in Volume II Appendix Tables B-28 and B-29. The arithmetic mean concentrations (used for background exposure estimation) for 2,3,7,8-TCDD and 2,3,4,7,8-PCDF were 0.01 and 0.03 pg/m3, respectively. Section 7.2.3.9. below discusses the use of this compilation to craft a profile of air concentrations that might be typical of rural, background settings where cattle are raised. Evidence suggests that urban air concentrations are 4-6 times higher than rural air concentrations. If so, than 2,3,7,8-TCDD and 2,3,4,7,8-PCDF concentrations in a rural environment might 0.002 and 0.006 pg/m3.
The on-site source category was demonstrated using concentrations of 1.0 ng/kg (ppt) for each example compound. This low concentration was assigned based on reports by researchers who measured concentrations of dioxin-like compounds in what they described as "background" and "rural" soils - they found non-detects to concentrations in the low ppt level. Modeled air concentrations of the example compounds 2,3,7,8-TCDD and 2,3,4,7,8-PCDF resulting from this level in soil were in the 10-5 pg/m3 range. For the stack emission source category demonstration, total (vapor + particle phases) concentrations of 2,3,7,8-TCDD simulated to arrive at points between 0.2 and 50 km were between 10-7 to 10-6 pg/m3. The off-site soil source category evaluated the impact of elevated soil concentrations to exposure sites that were located distant from the site of contamination. The example scenario demonstrating this source category had concentrations of this dioxin and furan congener set at 1 ppb, three orders of magnitude higher than the 1 ppt of the on-site source category demonstration scenarios. Air concentrations predicted in these example scenarios were in the 10-3 pg/m3 range.
Only this air concentration from the off-site soil contamination is generally in line with urban air concentrations of 2,3,7,8-TCDD, and/or a hypothesized rural air environment. It is at least plausible that elevated concentrations in soil would result in air concentrations that are in the same range as found in urban environments. A model result that would have questioned the model validity would have been, for example, that air concentrations resulting from soils of high concentrations would greatly exceed, or be very much lower, than urban air concentrations. In the same vein, it is certainly reasonable that air concentrations resulting from a single stack emission with generally a low release rate of 2,3,7,8-TCDD should be much lower than urban air concentrations.
It is not that clear that emissions and resulting air concentrations above soils at background levels should be lower by up to 2 orders of magnitude lower than what is hypothesized to occur in background setting. The argument has been made in Volumes I and II of this assessment that emissions from tall industrial stacks, followed by long range transport, are the ultimate source of these compounds in rural environments where the food supply is produced. The question remains as to how much of the contaminant in rural air is due to annual emissions and long range transport versus emissions from the soil reservoir source. If the modeling of this assessment is correct, than soils contribute very little to rural air concentrations. However, other evidence developed in this assessment suggests that the soil release and dispersion algorithms of this assessment may be underestimating air concentrations. One piece of that evidence is discussed in the next section below. Plant/soil ratios, defined as the ratio of 2,3,7,8-TCDD concentration in plants divided by that in the soil, were found to be lower in model predictions as compared to literature values. Two possible hypotheses were offered below: 1) the model is underpredicting air concentrations resulting soil releases, and/or 2) plant:soil ratios derived in experiments are not only the result of soil related impacts, but also from distant sources of air-borne release and long range transport - i.e., the air reservoir is not solely explained by soil releases. One other possibility would be that the algorithms estimating air to plant transfers are not valid and estimating too low a transfer rate. However, the air to plant transfers algorithms were examined in the section further below, Section 7.2.3.9, describing an air-to-beef food chain validation exercise. There, air to plant transfers onto a leafy hay crop were examined with data and model was predicting hay concentrations right in line with observations.
In summary, three pieces of evidence suggest that the soil to air models, and/or the parameters values selected for this model, may be underestimating air concentrations. One is the comparison of predicted air concentrations for a background soil compared against air concentration data described above. The second is developed below where plant:soil ratios predicted by the model appear lower than measured under experimental conditions. Third, air-to-plant transfers appear to test well, leaving the soil-to-air algorithms questionable for predicting low plant:soil ratios.
7.2.3.8. Impacts of contaminated soils to vegetations
There have been several studies which have measured plant concentrations of 2,3,7,8-TCDD for plants grown in soils with known concentrations of 2,3,7,8-TCDD, and more recently, studies with plant and soil concentrations for dioxin toxic equivalents or dioxin congener groups. One quantity that can be estimated from these studies is a plant:soil contaminant concentration ratio. The plant:soil ratio equals the concentration in the plant divided by the concentration in soil in which the plant is growing. Concentration ratios predicted to have occurred can be compared against those that have been measured in the various studies.
These ratio comparisons can be considered model validations, although none of the experimental or field conditions for the literature studies were duplicated in this exercise. The literature articles measuring soil and resulting plant concentrations of dioxin-like compounds are summarized in Table 7-6. This table also includes concentration ratios,
Table 7-6. Summary of plant concentration versus soil concentration data for 2,3,7,8-TCDD.
Plant/Soil Contaminant
Concentrations Ratio Reference and Comments
I. Below-Ground Vegetations
54-167 ppt/ .01-.17 Wipf, et al., 1982; results are for 2,3,7,8-TCDD and greenhouse carrots grown in Seveso
1-5 ppb contaminated soil; the 54 ppt concentration listed was for carrot peels and inner portions; the 167 ppt listed includes the 54 ppt plus additional residues found in wash water and can be described as "unwashed" concentration; 96% of 167 ppt unwashed concentration includes that found in wash water (67%) and peels (29%).
0.8-9.2 ppb/ .24-1.73 Coccusi, et al., 1979; results are for 2,3,7,8-TCDD and carrots, potatoes, narcissus, and onions
2.7-8.3 ppb grown on contaminated soil the spring following the Seveso contamination; aerial plant part ratios were 0.25-0.40 - underground part ratios were 0.23-1.73; residues in contaminated plants were found to dissipate when contaminated plants transplanted to unpolluted soils; results show higher ratios than the Wipf, et al. (1982) noted above; results were expressed in fresh plant weight and fresh soil basis; very high ratios and plant impacts render these data suspect.
156-1807 ppt/ 1.00-2.40 Facchetti, et al., 1986; results are for 2,3,7,8-TCDD and bean and maize roots grown in indoor
160-752 ppt greenhouse pots and outdoor pots; unclear whether plant concentrations are fresh or dry weights. Data considered highly suspect due to very high ratios found and also reporting 16 and 37 ppt in roots when "blank" soil had 1.5 ppt (ratios of 10.7 and 24.7).
735 ppt/ 1.8 Young, 1983; results are for 2,3,7,8-TCDD and roots of grass and broadleaf plants at Eglin Air
411 ppt Force Base; unclear whether root concentrations are fresh or dry weight.
0.5-40.2 ppt/ .001-.3 Hulster and Marschner, 1991; results at right are for unpeeled potato tubers, in TEQ and dry
2-6000 ppt weight basis. Plant:soil ratio decreased as soil concentrations increased; highest ratios were at the 2.4 ppt low soil concentration. Peeled tuber concentration stayed below 0.5 ppt over all soil concentrations, indicating insignificant within plant translocation. Plant concentrations given in dry weight basis.
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Table 7-6. (cont'd)
Plant/Soil Contaminant
Concentrations Ratio Reference and Comments
0.2-6.0 ppt/ .00001-.009 Hulster and Marschner, 1993a. Results are for potato tubers, peeled and unpeeled, and for potato
328-12,800 ppt shoots, results for TEQ and in dry matter terms. Concentrations for peeled potato tubers stayed consistently less than 0.5 ppt, despite soil concentrations, while shoots and unpeeled tubers increased as concentration increased. Plant:soil ratios remained relatively constant for tubers and shoots with soil concentration increases, leading authors to conclude that a soil/plant relationship exists for plants growing in the soil. Less transfer was noted for higher chlorination.
0.35, 0.96/ 0.02-0.07 Muller, et al., 1993a. Two plant/soil concentrations are for carrots in soil concentrations of 5 and
5, 56 ppt 56 ppt TEQ; carrot concentrations in dry matter and TEQ terms. Ratios decrease as concentrations increase; most of the concentration was in the peels.
II. Above-Ground Vegetations
(9-42 ppt)/ .0009-.0042 Wipf, et al., 1982; analysis of apples, pears, plums, figs, peaches, and apricots grown in
10 ppb Seveso, Italy year following contamination; apples, pears, and peaches showed >95% of whole fruit concentrations listed here was in the peels; analysis of vegetative samples in less contaminated areas showed non-detections at 1 ppt detection limit; reference was unclear as to whether reported concentrations in fruit was based on fresh or dry weight.
(8-9 ppt)/ .0008 Wipf, et al., 1982; concentrations listed were those found in sheaths of corn grown year following
10 ppb following Seveso contamination; none found in cobs and kernels at 1 ppt detection limit.
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Table 7-6. (cont'd)
Plant/Soil Contaminant
Concentrations Ratio Reference and Comments
(1-63 ppt)/ 0.003-0.35 Sacchi, et al., 1986; data was for: "aerial parts" of bean and maize plants, tritiated TCDD
(12-3300 ppt) TCDD amended soil with concentrations ranging as noted, taken at different intervals including 7, 34 and 57 days (one test), 17, 34, and 57 days (another test), 8 and 77 days, and 8 and 49 days, and in tests where soil was and was not amended with peat. Results showed increasing plant concentrations with increasing soil concentrations, but the ratio of plant to soil concentrations was inversely related to increasing soil concentrations (lowest ratios at highest soil concentrations). Soils without peat had higher ratios than soils with peat. Plant concentrations were fresh weight basis; high plant impact and trend for increasing impact over time renders these results suspect.
ND (DL=1 ppb)/ <0.017 Isensee and Jones, 1971; results are for mature oat and soybean tops, and oat grain and the
60 ppb bean of soybean, in soil treated with [14C]TCDD to achieve a concentration of 60 ppb - no residues of TCDD were found; ratios of 0.14 and 0.28 were found for 2,4,-dichlorophenol (DCP) in oat and soybean tops, and 0.20 for 2,7-dichlorodibenzo-p-dioxin (DCDD) in oat tops; trace amounts of DCP and DCDD were found in the bean of soybean.
(10-270 ppt)/ .02-0.66 Young, 1983; data was for 2,3,7,8-TCDD and above ground plant parts of perennial grasses and
411 ppt broadleaf plants grown on 2,4,5,-T treated soils. Unclear whether plant concentrations are fresh or dry weight basis. Soil concentration was average over 3 depth increments to 15 cm. Crown near soil surface at 270 ppt and 0.66 ratio was highest; plant tops had ratios of 0.02-0.17.
0.3, 0.1 ppt/ 0.00003, Muller, et al, 1993a. Result at right are for whole pear (0.3) and whole apple (0.1) dry weight
8750, 5215 ppt 0.00002 concentrations (article presented TEQs for two pears from one tree which were averaged, and one apple, and for fresh weight; dry weight was estimated assuming 12% dry matter in pears/apples) and the average concentration over 70 cm (article supplied concentrations for the 0-30 and 30-70 cm depths). Article also provided peel and pulp results and results for congener groups. Article concluded: soil levels were not correlated to fruit concentrations and therefore fruits were impacted by airborne contamination, and that concentrations were higher in peel than in pulp.
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Table 7-6. (cont'd)
Plant/Soil Contaminant
Concentrations Ratio Reference and Comments
0.1-0.6 ppt/ 0.00002- Hulster and Marschner (1993a). Results are for inner and outer leaves of lettuce, expressed as dry
326-5752 ppt 0.0008 matter, and in TEQs. Results indicate a drop in ratio as soil concentration increases, and unexpected small differences between inner and outer leaves.
4-38 ppt/ .001- Hulster and Marschner (1993a). Results are for hay, dry matter, and TEQs. Results indicate a drop
326-12,800 ppt .01 in ratio as soil concentrations increase.
<1 ppt/ .0001- Hulster and Marschner (1993a). Results are for grass and herbs, dry matter, and TEQs. Results
326-5752 ppt .0003 indicate a drop in ratio as soil concentrations increase. For above three entries, results are also given for congener groups. Authors conclude that: little correlation between soil and above ground plant concentrations, and that contamination is by atmospheric deposition.
<.01, .04/ <0.002 Muller, et al., 1993b. Results are for peas at soil concentrations of 5 and 56 ppt; pea
5, 56 ppt concentrations in TEQ and dry weight. Results for pods indicated more impact with ratios at 0.002-0.026. Ratios decreased as soil concentration increased.
0.32, 0.21 ppt/ .004- Muller, et al., 1993b. Results are for lettuce at soil concentrations of 5 and 56 ppt; lettuce
5, 56 ppt .064 concentrations in TEQ and dry weight. Little difference seen between inner and outer leaves, which was unexpected - outer leaves expected to be more impacted. Ratios decreased as soil concentration increased.
0.5-22.6 ppt/ .14- Hulster and Marschner, 1993b. Results are for zucchini fruit at two soil concentrations of 0.4 and
0.4, 148 ppt 2.5 148 ppt TEQ, fruit results are TEQ and dry weight. Results contradict conventional wisdom that above ground vegetation impact is from air only and mainly an outer surface phenomena; zucchini contamination was uniform throughout plant and plant:soil ratios highest ever found for above ground bulky fruits.
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Table 7-6. (cont'd)
Plant/Soil Contaminant
Concentrations Ratio Reference and Comments
0.6 ppt/148 ppt .004 Hulster and Marschner, 1993b. Results are for cucumber grown in soil at 147 ppt TEQ; cucumber results in TEQ and dry weight. Results are more in line with most other studies for above ground bulky fruit plant:soil ratios.
7.5 ppt/148 ppt .05 Hulster and Marschner, 1993b. Results are for pumpkin grown in soil at 148 ppt TEQ; pumpkin results in TEQ and dry weight. Results not as dramatic as for zucchini, but plant concentrations are ratio are still high.
0.4-1.9 ppt/ .0003- Hulster and Marschner, 1991. Results are for lettuce, in TEQ and dry weight. Experiments were
2.4-6000 ppt .3 conducted outdoors with soil covered by a water permeable polypropylene fleece. Plant concentrations showed little variation with large increases in soil concentration, and given the soil covering, this would strongly indicate little root to shoot translocation and that lettuce concentrations were the result of air to plant transfer.s
and separates sections for above and below ground vegetations.
In measuring both the soil and the plant concentration, several of the early literature articles, particularly those from Seveso (Wipf, et al., 1982; and Coccusi, et al., 1979) presumed that the soil in which the plant was growing was the ultimate source for the 2,3,7,8-TCDD contamination of above ground plant parts, if not from direct uptake than from deposition of suspended particles. However, recent research has concluded that the contamination of above ground plant parts is due principally to air-to-plant transfers (Hulster and Marschner, 1993a; Muller, et al, 1993a; Muller, et al., 1993b; Welsh-Paush, et al (1993); and others). These cited research efforts have concluded that there is no consistent relationship between soil concentrations of dioxin-like compounds and above ground vegetative concentrations of these compounds, which has led the researchers to conclude that air-to-plant transfers explain plant concentrations (a recent report did strongly imply a direct soil/plant for dioxin-like compounds for at least one family of above ground vegetables, the cucumber family (Hulster and Marschner, 1993b); this will be discussed below). This fact, coupled with the fact that sources of airborne contamination by dioxins include both distant sources and soil releases, make it difficult to compare literature reports of plant:soil contamination concentrations with those predicted by the soil contamination modeling of this assessment.
Recall that the "on-site" soil source modeling presumes that air concentrations and depositions to which the plant are exposed originate only from the soil in which the plant is growing. One would expect that the modeled plant:soil ratio for above ground plant parts would be lower than plant:soil ratios measured in field settings, since the field measured ratios are influenced by more than just the soil releases into the air.
On the other hand, the literature is consistent in concluding that soil provides the source for underground soil to root transfers. For this reason, Table 7-6 and the following discussions distinguish between above and below-ground vegetations.
The following plant:soil contaminant concentration ratios were estimated for the two scenarios demonstrating the on-site source category in Chapter 5, Scenarios 1 and 2: below ground vegetables - 7x10-3 (dry weight basis, assuming vegetables are 15% dry matter), above ground vegetables/fruit - 7x10-5 (dry weight basis, assuming vegetables/fruits are 15% dry matter), grass - 6x10-3 (dry weight), and feed 3x10-3 (dry weight). Some observations from experimental results found in the literature, and comparison with the results of the model, are:
1) The largest body of consistently developed experimental data on soil-plant relationships of dioxin-like compounds comes from a research group in Germany who have published numerous articles for different vegetations and experimental conditions in the 1990s (Hulster and Marschner, 1991; Hulster and Marschner, 1993a,b; Muller, et al., 1993a,b). Some of the earlier literature showed much higher impacts to vegetations than measured by these German researchers (Coccusi, et al., 1979; Facchetti, et al., 1986; Young, 1983), which in the judgement of the authors of this EPA assessment, renders them suspect. One early report, that of Wipf, et al. (1982), does show results consistent with the German research. The observations following will focus mainly on this research from Germany.
2) Experimental results for both above and below ground vegetations suggest that plant:soil ratios decrease as soil concentration increases. For below ground vegetations, this suggests that the movement into plants is not a passive and unimpeded process occurring with transpiration water, for if it were, plant:soil ratios would be constant as concentration increases. For above ground vegetations, the observations given above that air-to-plant transfers and not soil-to-plant transfers better explain plant concentrations, and that air concentrations include soil releases as well as long term transport, leads one to conclude that a consistent relationship between soil concentrations and plant concentrations is not to be expected. An explanation for this trend for below ground vegetative trends could not be found.
The models of this assessment - soil to below ground vegetation, soil to air to above ground vegetation, and air to above ground vegetation - cannot duplicate these observed trends, that is, the models will not show a decrease in plant:soil ratios as soil concentration increases. Above and below ground vegetation concentrations are a linear function of a biotransfer factor and an appropriate media concentration - air, soil water. For particle depositions, no transfer parameters are used, but plant concentrations are a linear function of model inputs, including deposition rates, plant interceptions and yield, and a plant washoff factor. Therefore, plant concentrations will be a linear function of soil concentrations for the soil source categories.
3) Plant:soil ratios for below ground vegetables for soil concentrations in the low ppt range would appear to be in the 10-1 to 10-2 range (Muller, et al, 1993; Hulster and Marschner, 1991), in contrast to the 0.007 predicted by the model. Much higher ratios were found in the earlier studies (Coccusi, et al., 1979; Facchetti, et al., 1986; Yount, 1983), which earlier had been speculated as being questionable. One earlier study, that of Wipf, et al. (1982), does report ratios similar to these later studies, as noted above. At higher soil concentrations in the sub to low ppb range, plant soil ratios are more in the 10-4 to 10-3 range (Hulster and Marschner, 1993a; Hulster and Marschner, 1991), even lower than the modeled 0.007 ratio.
4) The results for above ground bulky vegetations, fruits and vegetables, indicate plant:soil ratios that are lower than plant:soil ratios for bulky below ground vegetations, for comparable soil concentrations. The evidence for this observation is best found in the Hulster and Marschner (1993a) concurrent experiments for potatoes and pears/apples, as well as the earlier work of Wipf, et al. (1982) for several fruits and carrots. The same trend is also found for the grass results for 2,3,7,8-TCDD given in Young (1983). This trend is also duplicated by the models, which showed two orders of magnitude difference in below ground as compared to above ground vegetations. The plant:soil modeled ratio of 7*10-5 is similar to ratios found when the soil concentration was in the hundreds to thousands of ppt (Hulster and Marschner, 1993a). However, other data, particularly for leafy vegetations such as hay, grass, and lettuce, and for lower soil concentrations, indicate a soil:plant ratio of 10-3 to 10-2. Two possible explanations are offered for this trend: 1) above ground vegetations in experiments are likely to be impacted by not only soil releases, but distant sources of release, and/or 2) the models could be underpredicting air concentrations resulting from soil releases.
4) Several of the articles, both from the German work and the earlier work, noted that most of the concentration was in the outer portions of the below and above-ground vegetations, and not the inner portions. Despite significant increases in soil concentration from the ppt to the ppb range, inner potato tuber concentrations remained constant (Hulster and Marschner, 1991, 1993a). This evidence was the principal justification for the use of the empirical adjustment factors termed VG for soil to below ground transfers, VGbg, and vapor-phase air transfers to bulky above ground vegetations, VGag. The chemical-specific empirical transfers factors for both of these transfers were developed in laboratory experiments with several chemicals using thin vegetations - solution phase transfers to barley roots for below ground vegetation concentrations, and vapor phase transfers to azalea leaves for vapor phase transfers. For the dioxin-like compounds, direct use of these transfer factors would be most appropriate for the outer few millimeters, perhaps, of below and above ground bulky vegetations. The assignment of a VG of 0.01 for bulky above and below ground vegetations was based on an outer surface volume to whole plant volume ratio for a common vegetation such as a carrot or an apple. A VG of 1.00 was used for grass, since that is a thin vegetation.
Further evidence for the above ground VG came from a recent study by McCrady (1994), who measured the uptake rate constants of vapor-phase 2,3,7,8-TCDD to several vegetations including grass and azalea leaves, kale, pepper, spruce needles, apple, and tomato. The uptake rate for the apple divided by the uptake rate for the grass leaf was 0.02 (where uptake rates were from air to whole vegetation on a dry weight basis). For the tomato and pepper, the same ratios were 0.03 and 0.08. The VGag was 0.01 for fruits and vegetables in this assessment. McCrady (1994) then went on to normalize his uptake rates on a surface area basis instead of a mass basis; i.e., air to vegetative surface area uptake rate instead of an air to vegetative mass uptake rate. Then, the uptake rates were substantially more similar, with the ratio of the apple uptake rate to the grass being 1.6 instead of 0.02; i.e., the apple uptake rate was 1.6 times higher than that of grass, instead of 1/50 as much when estimated on an air to dry weight mass basis. The ratios for tomato and pepper were 1.2 and 2.2, respectively. Therefore, since the Bvpa in this assessment is an air to plant mass transfer, the McCrady experiments would appear to justify the use of an above-ground VG of a magnitude less than 0.10.
5) A recent experiment by the Hulster and Marschner (1993b) on vegetations of the cucumber family contradicted the conventional wisdom that direct soil to root to above ground plant impact would not occur for the dioxin-like compounds. Their results were most striking for zucchini, which showed uniform plant concentrations from inner to outer portions of the zucchini fruit, and the highest whole fruit concentrations and plant:soil ratios they had ever measured, despite careful experimental conditions which physically isolated the fruit from the soil. Pumpkins also showed high plant contamination and plant:soil ratios, with more expected plant concentrations measured for the cucumber. No explanation was offered for these results. It was assumed for this exposure assessment that the fruits and vegetables for human consumption, and the grasses, hay, and other vegetations animals consume, would not follow this pattern.
A principal conclusion that can be drawn from this examination is that the plant:soil contaminant concentration ratios developed by the soil contamination models of this assessment may be lower by perhaps an order of magnitude or more than measured ratios at lower soil concentrations, in the low ppt range, whereas they may be more in line and even higher when soil concentrations are the hundreds of ppt to the ppb range. This trend appears to hold for both above and below ground vegetations. This difference in the comparison of modeled and observed ratios as the concentration changes is because the data shows that plant:soil ratios decrease as soil concentrations increase. This cannot be duplicated by the model since the plant concentrations are a linear function of the source strength terms - the soil, soil water, or air concentrations and deposition. An explanation for this observed trend could not be found. The observation that plant:soil ratios for above ground vegetations are higher in the literature at lower soil concentrations (and more typical of background rather than heavily contaminated soils) as compared to the modeled ratios, has to be carefully considered. Two explanations are offered. For experiments conducted outdoors, the source of air reservoirs of dioxin-like compounds are the soil in which the plant is growing as well as from distant sources and long-term transport. Also, it is possible that the model is underpredicting air concentrations and hence underpredicting air to plant transfers.
7.2.3.9. A validation exercise for the beef bioconcentration algorithm
The premise of this modeling exercise to test the beef food chain model for dioxin-like compounds is that air-borne reservoirs of these compounds in rural environments are the "source term" explaining concentrations found in beef. Further, this exercise probably would not qualify as a validation exercise in the traditional sense. Most environmental model validation exercises rely on data obtained from a single site. This exercise instead develops a representative rural air concentration profile and attempts to model a profile of average beef concentrations.
The model structure, from air to beef, is shown in Figure 7-3. The algorithms for these components, and assignment of model parameters, were described in Chapter 4, and are very briefly summarized here. The "observed" source, or independent, term in this modeling exercise are the air-borne concentrations of dioxin-like compounds shown at the top of Figure 7-3, and the "predicted", or dependent, results are the concentrations in
whole beef shown at the bottom of this figure. Both these quantities are developed from reported United States measurements. Section 7.2.3.9.1 below describes the generation of these concentration profiles. Section 7.2.3.9.2 summarizes model algorithms and parameter assignments. Section 7.2.3.9.3. presents the results and discussions from this exercise.
7.2.3.9.1. Air and beef concentrations
Very little data are available worldwide on air concentrations of individual dioxin-like congeners in a rural setting. This is the kind of air concentration data that would be needed for this exercise. An evaluation of ambient air monitoring studies in the United States conducted for Volume II of this assessment showed that nearly all of the data was from urban or suburban settings. The purpose of this compilation was to determine an ambient air concentration suitable for estimating inhalation exposures to dioxin-like compounds. Measurements which were attributed to a nearby identifiable source, such as an incinerator, were not considered for this effort. From several studies around the country, a total of 84 air samples were available, from which a mean TEQ level of 0.095 pg/m3 was determined. Further detail on this compilation can be found in Chapter 4 of Volume II.
There are a few references which do have congener-specific data which might be characterized as rural. One is outside of United States in Sweden (Broman, et al., 1991). Air samples were taken in four areas, ranging from the Stockholm urban area to the open coastal area of the Baltic Sea. Results indicate lower TEQs when going from the urbanized area to the remote areas. The Stockholm city center was 0.024 pg TEQ/m3, a "suburb" was 0.013 pg TEQ/m3, a "countryside remote" area was 0.0044 pg TEQ/m3, and an "open coastal" area was 0.0026 pg TEQ/m3. Twenty-five PCDD/F concentrations were listed at the fg/m3 level (i.e., 0.001 pg/m3).
The only reference found for the United States with congener specific data for an area described as rural was from Ohio (Edgarton, et al., 1989). Six sites were tested, one of which might be considered rural. The data contained many non-detects, with detection limits between 0.033 to 0.82 pg/m3, although most non-detects had detection limits less than 0.3 pg/m3. The following TEQ concentrations were derived only from the positive listings: two sites in Akron - 0.077 and 0.079 pg TEQ/m3, two sites in Columbus - 0.092 and 0.179 pg TEQ/m3, a site near a highway - 0.065 pg TEQ/m3, and a rural site in a town called Waldo - 0.045 pg TEQ/m3. Like the data from Sweden, one can see a trend for lower concentrations in the Waldo site as compared to the sites in Columbus and Akron.
Other references did contain other pertinent data, such as total concentrations, TEQ concentrations, or congener group concentrations, in rural and urban settings. Eitzer and Hites (1989) took data from Bloomington, Indiana and a remote area in Wisconsin known as Trout Lake. TEQ concentrations were not given, but total congener group concentrations were reported. The sum of congener group concentrations, or total concentrations of dioxins and furans, equaled 2.2 pg/m3 for Bloomington, and 0.51 pg/m3 for Trout Lake. This 0.51 pg/m3 total concentration is similar to the total concentration found in the "countryside remote" area in Sweden discussed above, which is 0.41 pg/m3 (TEQ concentration was 0.0044 pg/m3, as noted above).
In an evaluation of air, soil, sediment, and fish in Elk River, Minnesota, a rural setting, again total congener concentrations in the air were reported (Reed, et al., 1990). Concentrations for three sites and for two sampling dates, one in the winter and one in the summer, were available. Two of the three sites were in rural settings and the third was near a refuse derived fuel incinerator. Total concentrations for the two rural sites in winter and in summer were 2.29 and 2.91 pg/m3 in winter, and 0.58 and 0.38 pg/m3 in summer. For the third site near the incinerator, winter and summer concentrations were 15.2 and 0.35 pg/m3, respectively. The average of the four data points for rural settings was 1.54 pg/m3, while the average of the two data points near the incinerator was 7.78 pg/m3.
Finally, Maisel and Hunt (1990) list TEQ concentrations only for monitoring networks including: a Connecticut coastal location described as urban (measurements described as "wintertime"), a southern California urban setting ("annualized"), and a central Minnesota rural setting ("annualized"). While not identifying it as such, this central Minnesota setting could be the one described above in Elk River, Minnesota. The TEQ concentrations for the two urban and one rural setting were: 0.092, 0.091, and 0.021 pg TEQ/m3.
Key points from this literature summary are:
1. Congener specific profiles for rural settings in the United States are generally not available. Based on several studies encompassing 84 data points with specific congener concentrations which best represent urban/suburban settings, but are not near identified emission sources, a mean TEQ air concentration of 0.095 pg/m3 is estimated.
2. Studies are available which do provide side by side data on urban and rural settings, although the literature references only list congener group concentrations or total TEQ concentrations (with the exception of the Edgarton, et al. (1989) described above). What this summary shows is that rural air concentrations of dioxin-like compounds appear to be 4-6 times lower than in urban settings, and that a TEQ concentration for rural settings appear to range from 0.004 to 0.04 pg/m3.
In order to develop a profile of air concentrations that will be considered representative of rural settings, what will be done, therefore, is to take the profile of congener-specific air concentrations for urban/suburban settings leading to a TEQ concentration of 0.095 pg/m3, and divide each concentration by 5. The resulting TEQ concentration is 0.019 pg/m3. The total concentration of PCDD/Fs in this rural profile equals 1.09 pg/m3. A uniform division by five for all congeners essentially assumes that the ultimate sources for an urban and a rural profile of air concentrations are the same. The specific concentrations used are shown in Table 7-7.
A review of data on concentrations of dioxin-like compounds in beef showed that very limited data was available worldwide, much less United States. Only three studies contained congener-specific data of dioxins and furans in beef in United States. In one study beef samples were composited with veal and the results described as beef/veal. The three studies only encompassed 14 samples. These studies include one conducted by the California Air Resources Board (CARB; Stanley and Bauer, 1989), the results of background analysis from a study conducted by the National Coalition for Air and Stream Improvement (NCASI; the study described in Lafleur, et al., 1990) and a survey of foods conducted in New York by Schecter et al. (1993).
These were the data used to estimate background exposures to dioxins in beef in Chapter 5 of Volume II. The total TEQ for beef and veal was calculated by using one-half the detection limits reported by the researchers to represent the concentration of nondetectable CDD/F congeners in the samples. Using this methodology, the TEQ concentration was estimated to be 0.48 ng/kg (ppt) for beef and veal on a wet weight basis. If nondetectable concentrations are assumed to be zero, the estimated TEQ for beef and veal is 0.29 ppt. The average whole beef congener-specific concentrations assuming non-detects were one-half the detection limit are to be used to represent beef concentrations, and they are shown in Table 7-7. All studies reported concentrations as lipid-based concentrations. Where lipid fractions were not supplied, 19% lipid content for beef was assumed to estimate whole beef concentrations.
It is important to note that the United States samples came from commercial food outlets (grocery stores, e.g.). This fact will be used to imply that the data represents beef cattle that went through a feedlot fattening process prior to slaughter. As will be discussed below, this has implications regarding final concentrations.
Table 7-7. Observed air and beef concentrations, and fate parameters for individual dioxin and furan congeners.
Parameters for Bvpa Parameters for Vapor/Particle Partitioning Observed Data
Compound H log Kow Bvpa Tm, K VPs, atm Vapor/Particle BCF air, pg/m3 beef, ppt
2378-TCDD 1.6*10-5 6.64 1.0*105 578 9.7*10-13 0.55/0.45 4.32 0.002 0.03
12378-PeCDD 2.6*10-6 6.64 6.3*105 513 1.3*10-12 0.26/0.74 4.16 0.006 0.22
123478-HxCDD 1.2*10-5 7.79 2.3*106 547 1.3*10-13 0.07/0.93 2.02 0.005 0.26
123789-HxCDD 1.2*10-5 7.79 6.9*105 516 6.5*10-14 0.02/0.98 2.24 0.007 0.84
123678-HxCDD 1.2*10-5 7.30 6.9*105 558 4.7*10-14 0.04/0.96 1.74 0.010 0.21
1234678-HpCDD 7.5*10-6 8.20 1.0*107 538 4.2*10-14 0.02/0.98 0.36 0.116 1.92
OctaCDD 7.0*10-9 7.59 2.4*109 598 1.1*10-15 0.00/1.00 0.52 0.586 2.91
2378-TCDF 8.6*10-6 6.53 1.5*105 500 1.2*10-11 0.71/0.29 0.94 0.023 0.06
23478-PeCDF 6.2*10-6 6.92 5.3*105 469 4.3*10-12 0.30/0.70 3.10 0.010 0.04
12378-PeCDF 6.2*10-6 6.79 3.8*105 499 3.6*10-12 0.42/0.58 0.73 0.006 0.21
123478-HxCDF 1.4*10-5 7.30 5.9*105 499 3.2*10-13 0.06/0.94 2.34 0.012 0.51
123678-HxCDF 6.1*10-6 7.30 1.4*106 506 2.9*10-13 0.06/0.94 2.00 0.012 0.06
123789-HxCDF 1.0*10-5 7.30 8.3*105 520 3.7*10-13 0.11/0.89 2.00* 0.003 0.06
234678-HxCDF 1.0*10-5 7.30 8.3*105 512 2.6*10-13 0.07/0.93 1.78 0.009 0.07
1234678-HpCDF 5.3*10-5 7.90 6.8*105 509 1.8*10-13 0.04/0.96 0.41 0.042 0.40
1234789-HpCDF 5.3*10-5 7.90 6.8*105 495 1.4*10-13 0.03/0.98 0.99 0.006 0.13
OctaCDF 1.9*10-6 8.80 1.7*108 532 4.9*10-15 0.00/1.00 0.20 0.034 0.22
Column headings are:
H: Henry's Constant, atm-m3-mole Tm: Melting point temperature, K
log Kow: log octanol water partition coefficient Ps: Crystalline solid vapor pressure, atm-1
Bvpa: air-to-leaf transfer factor, unitless Vapor/Particle: fraction of total reservoir in vapor and particle phases
BCF: beef biotransfer factor, unitless air: total reservoir of congener in air, pg/m3
beef: whole beef observed concentrations, ng/kg
*
McLachlan, et al. (1990) did not provide data on 123789-HxCDF; the value for 123678-HxCDF was used instead.7.2.3.9.2. Summary of algorithms, key assumptions, and parameter values
All parameters associated with individual congeners are shown in Table 7-7, and all parameters not specific to the congeners are shown in Table 7-8. Following now are summaries of the algorithms and key assumptions of this exercise. Many of them have been described in earlier chapters of this Volume and Volume II, and are not repeated here.
1. Partitioning total concentrations into a vapor and a particle phase
As shown in Figure 7-3, this is the first key step in this modeling exercise. Chapter 3 of this volume described air monitoring studies which reported the partitioning of dioxins into a particle and a vapor phase. Arguments were presented as to why these studies would likely overestimate the portion in the vapor phase. Because of this, a theoretical model for estimating the fraction of total concentration in the particulate and vapor phases was recommended for use in this assessment. The model of Bidleman (1988) was presented and discussed in Chapter 3, and will be used here as well. Table 7-7 presents the vapor and particle fractions assumed in this assessment, based on the Bidleman model.
2. Particle Depositions to Vegetations and Soils
Chapter 4 described the wet and dry particle deposition algorithm used for this assessment. The dry deposition algorithm and the key parameter assignment of a dry deposition velocity of 0.2 cm/sec will be used for this exercise without change. However, the wet deposition algorithm described in that chapter includes assignment of an annual rainfall amount with a washout factor. This is more appropriate for a site-specific application, and because this exercise is based on a "representative" rural profile of air concentrations and an average beef concentration profile derived from three locations in the United States, a simplification of the wet deposition algorithm is used in this exercise. This simplifications is based on the measurements made by Koester and Hites (1992). They measured wet deposition of total dioxins at two sites in Indianapolis and Bloomington, Indiana, and generally found wet deposition to be comparable to dry deposition. Specifically, the estimated annual wet deposition of dioxins at Indianapolis was equal to 0.7 times dry deposition, while at Bloomington, wet deposition was 1.3 times dry deposition. Therefore, it will be assumed that wet deposition equals dry deposition in this exercise. Crop yields and interceptions which were used for the demonstration scenarios of Chapter 5 are used for the deposition algorithms here as well.
Table 7-8. Model parameters used for all dioxin-like congeners.
Parameter Description Value
I. For Vapor/Particle Partitioning
C constant to estimate sorbed fraction
in Equation (?), atm-cm 1.7*10-4
T ambient air temperature, ° K 298.1
D Sf/R entropy of fusion/universal gas constant, unitless 6.79
ST average total surface area of aerosol particles
relative to average total volume of air, cm2/cm3 3.5*10-6
VT average total volume of aerosol particles
per volume of air, cm3/cm3 3*10-11
II. Particle Depositions
kw first-order plant weathering constant, yr-1 18.01
ks first-order soil dissipation constant, yr-1 0.0693
Yg yield of grass, kg/m2 0.15
Ig interception fraction of grass 0.35
Yh/s yield of hay/silage/grain 0.63
Ih/s interception fraction of hay/silage/grain 0.62
Vd velocity of particle deposition, m/sec 0.002
M mass of mixing soil, kg/m2 10
Rw retention of wet deposition on vegetations, fraction 0.30
III. Vapor Transfers
VGgr empirical correction factor for grass, unitless 1.00
VGh/s empirical correction factor for hay/silage/grain, unitless 0.50
IV. Bioconcentration
Bs bioavailability of contaminant on the soil vehicle
relative to the vegetative vehicle, unitless 0.65
DFs cattle soil diet fraction 0.04
DFg cattle grass diet fraction 0.48
DFh/s cattle hay/silage/grain diet fraction 0.48
V. Other
fat content of beef 0.19
concentration reduction due to feedlot fattening 0.50
assumption: wet deposition equals dry deposition
The soil deposition algorithm remains unchanged from the structure and parameter assignments described in Chapter 4 and demonstrated in Chapter 5.
3. Vapor Phase Transfers to Vegetations
The key parameters for this algorithm include the air-to-leaf transfer factor, the Bvpa, and the empirical adjustment parameter, VG, which reduces vapor transfers considering the difference in the thin azalea and grass leaves used in experiments to derive the Bvpa and the bulky and protected vegetations of the cattle diet, such as silages as grains. The values of these parameters are the same ones used in Chapter 5.
4. Bioconcentration Model
The bioconcentration model includes assignment of the congener-specific bioconcentration factor, BCF, and the soil bioavailability parameter, Bs. The parameter assignments for these parameters are the ones which were developed in Chapter 4, used for the demonstration scenarios of Chapter 5, and shown on Tables 7-7 and 7-8.
5. Dietary Exposure of Cattle to Dioxins
The final key areas in this model are the assumptions concerning cattle exposure to dioxin-like compounds through their diet. A related key issue is the impact of feedlot fattening on final beef concentrations. The general diet profile used for the demonstration scenarios for beef concentration estimations in Chapter 5 is used here as well. This included an assumption of equal proportions of pasture grass and non-grass feed such as hay, silage, or grain, and a small amount of incidental soil. As discussed in Chapter 4, a 4% soil ingestion rate was assumed, leaving 48% each for pasture grass and the second category of cattle vegetation intake, abbreviated hay/silage/grain. Chapter 4 also discussed the impact of feedlot fattening. The demonstration scenario of Chapter 5 did not include feedlot fattening since the scenario was one of a farmer home slaughtering for personal consumption. For this exercise, however, it is likely that the commercial beef samples from which the "observed" concentration profile was derived came from cattle which had undergone a period of feedlot fattening. Chapter 4 summarized modeling efforts which attempted to characterize the impact of a period of fattening assuming residue-free intake for a period of 120 days. Based on their results, these modeling efforts hypothesized that such a diet regime would reduce fat concentrations by one-half. This will be the assumption used here as well; beef concentrations estimated using all the modeling described above will be halved as a final step in the modeling process.
7.2.3.9.3. Results and discussion
A final comparison of predicted versus observed whole beef concentrations is shown in Table 7-9. Total TEQ concentrations compare favorably, with observed total TEQ at 0.48 ppt and predicted TEQ at 0.36 ppt. The congeners of most toxicity also had the best match of predicted and observed concentrations: 2,3,7,8-TCDD - 0.03 ppt observed and 0.03 ppt predicted; 1,2,3,7,8-PCDD - 0.22 observed and 0.27 ppt predicted; 2,3,4,7,8-PCDF - 0.21 ppt observed and 0.17 ppt predicted. The largest discrepancies, an order of magnitude and more, were for two of the HxCDDs and for all HpCDD/Fs and OCDD/Fs. The total concentrations did not compare as well as the TEQ concentrations, with observed total whole beef concentration of 8.15 ppt and predicted at 2.13 ppt.
As a way of further examining these results, limited examinations are now presented on the two key components of this food chain model - the air to vegetation algorithm, and the air to soil algorithms.
One data set in the literature allows some limited comparisons between model predictions and observations of vegetation concentrations. This data was from a rural setting in Elk River, Minnesota (Reed, et al., 1990). This site was mentioned in the section above describing the derivation of the rural air concentration profile. The reference listed air concentrations by congener grouping for a rural setting (2 air sampling sites) and near an incinerator (1 site). It was noted that the average annual air concentrations near the incinerator was about 5 times higher than the average annual air concentration at the two rural sampling stations. The total PCDD/F air concentration in the rural setting was estimated at 1.54 pg/m3. The corresponding TEQ concentration cannot be estimated without knowing the concentration of the congeners with non-zero toxicity. Therefore, a comparison to the crafted 0.019 pg/m3 concentration for the rural setting in this paper cannot be made. However, a data set earlier described from Sweden (Broman, et al., 1990), listed a total concentration of 0.42 pg/m3 and a corresponding TEQ concentration of 0.004 pg/m3 for a rural Swedish countryside. This ratio of 100 between total and TEQ concentrations indicates that the Elk River total concentration of 1.54 pg/m3 may translate to a TEQ concentration around 0.015 pg/m3, which would be consistent with the 0.019 pg TEQ/m3 developed in this paper.
This study also took samples of vegetations in this rural setting, including two hay and two corn samples. The limits of detection for these vegetation samples varied
Table 7-9. Results of validation exercise showing observed and predicted concentrations of dioxin-like compounds in whole beef.
Observed whole beef Predicted whole beef
Compound concentrations, ng/kg1 concentrations, ng/kg
2378-TCDD 0.03 0.03
12378-PCDD 0.22 0.27
123478-HxCDD 0.26 0.10
123678-HxCDD 0.84 0.03
123789-HxCDD 0.21 0.04
1234678-HpCDD 1.92 0.29
OCDD 2.91 0.29
2378-TCDF 0.06 0.46
12378-PCDF 0.04 0.07
23478-PCDF 0.21 0.17
123478-HxCDF 0.51 0.08
123678-HxCDF 0.06 0.13
123789-HxCDF 0.06 0.04
234678-HxCDF 0.07 0.07
1234678-HpCDF 0.4 0.04
1234789-HpCDF 0.13 0.01
OCDF 0.22 0.01
TOTAL CONCENTRATION 8.15 2.13
TEQ CONCENTRATION 0.48 0.36
between 0.31 and 6.5 ppt on a congener-specific and site-specific basis. With vegetation concentrations predicted to be in this range generally, the data therefore cannot be rigorously informative. The congener found with the highest concentration is OCDD, found at 72 (site 1) and 170 (site 2) ppt in two corn samples, and 270 (site 1) and 300 (site 2) ppt in two hay samples. In addition to this higher finding in the hay samples, generally more positives were detected in hay rather in corn. This is consistent with discussions in this paper indicating that vegetation concentrations of dioxin-like compounds is a surface phenomena with little within plant translocation. Hay, in this observation, is considered a leafy vegetation, whereas corn is considered a bulky vegetation.
Table 7-10 lists the average congener specific hay concentrations observed in Elk River (the average of two hay samples, with non-detects counted as 0.0 when one of the two samples had a positive, and just listed as ND when both hay samples showed non-detects) compared against the model's predicted concentrations in grass. This is felt to be a valid comparison. It assumes that hay alone is reasonably similar to grass in that both are "leafy" vegetations and would be modeled similarly in the framework of this paper.
What is now available to interpret and analyze are the predicted and observed beef concentrations, the predicted and observed leafy vegetation concentrations, and further model trends. Several observations are now summarized based on these analyses:
1) Given the range of the detection limit, 0.31-6.5 ppt for the hay sampling, the model's predictions of grass concentrations are generally consistent with observations, with the exception of the OCDD and OCDF concentrations. It is noted that the second highest congener observation of 30 ppt of 1,2,3,4,6,7,8-HpCDD is matched by the model's prediction of 20.7 ppt for 1,2,3,4,6,7,8-HpCDD.
2) The analysis of the OCDD and OCDF results for hay is very telling. First, it is noted that the crafted rural air concentrations of these two congeners matches very well with the observed air concentrations at this Elk River site: OCDD observed at 0.5 pg/m3 and crafted at 0.57 pg/m3; and OCDF observed at 0.09 pg/m3 and crafted at 0.034 pg/m3 (note: the observed concentrations for OCDD/F congeners is the average of four listed concentrations of OCDD/F congeners in Reed, et al. (1990) - rural sites 1 and 2 and winter and summer listings). Since the crafted air concentrations match well with the observed air concentrations, one would hope that the vegetative concentrations also match. An analysis of why they did not indicates the importance of vapor phase contributions to vegetative concentrations. According to the application of the Bidleman (1988) approach for estimating the bound fraction, f , in the air, both these congeners were assigned a f of 1.00. In fact, using the OCDD/F vapor pressures and melting points, these f values were both 0.998. If one allows for the possibility that f for OCDD/F could be less than one, and calibrates f for OCDD/F for this exercise, one can show that small reductions in f result in better predictions of both grass and beef concentrations. Recall that the observed "grass" concentrations are, in fact, the hay concentrations found at Elk River, Minnesota,
Table 7-10. Comparison of concentrations of dioxin-like compounds found in hay in a rural setting with model predictions of grass concentrations.
Observed hay Predicted grass
Compound concentration, ng/kg1 concentrations, ng/kg
2378-TCDD ND 0.1
12378-PCDD ND 0.9
123478-HxCDD ND 0.7
123678-HxCDD 1.2 0.2
123789-HxCDD ND 0.2
1234678-HpCDD 30 21.0
OCDD 285 6.0
2378-TCDF ND 7.2
12378-PCDF ND 1.4
23478-PCDF ND 0.8
123478-HxCDF ND 0.5
123678-HxCDF ND 0.9
123789-HxCDF ND 0.3
234678-HxCDF ND 0.5
1234678-HpCDF 5.4 1.4
1234789-HpCDF ND 0.1
OCDF 7.5 0.4
1
Observed data from Reed, et al. (1990). Concentrations listed are the mean of two observations for hay grown in rural settings. ND assumed to be zero for calculation of means. Limits of detection described in Reed, et al. (1990) as ranging between 0.31 and 6.5 ppt, on a congener-specific and site-specific basis.
and that the observed beef concentrations are those which were generated using available data from around the country. Table 7-11 shows the results of a calibration, where f is first 1.00 as initially assumed, and then calibrated so that grass/hay and subsequently beef are more in line. As seen, the calibrated f are 0.9998 for OCDD and 0.998 for OCDF, and the grass and beef concentrations predicted are now much closer to observations.
The main reason for these very large differences in model predictions of hay
Table 7-11. Calibration exercise showing improvements in grass and beef concentrations when the fraction sorbed parameter, f , drops minutely below 1.00 for OCDD and OCDF.
I. Uncalibrated: f = 1.00 for OCDD and OCDF
grass/hay, ng/kg (ppt) whole beef, ng/kg (ppt)
Pred. Obs. Pred. Obs.
OCDD 6.0 285 0.29 2.91
OCDF 0.4 7.5 0.01 0.22
II. Calibrated: f = 0.9998 for OCDD and 0.998 for OCDF
grass/hay, ng/kg (ppt) whole beef, ng/kg (ppt)
Pred. Obs. Pred. Obs.
OCDD 237 285 8.51 2.91
OCDF 10.2 7.5 0.14 0.22
concentrations with seemingly small differences in the amount assumed to be in the particle phase is that the air-to-leaf transfer factor, the Bvpa, is 2 to 4 orders of magnitude higher for OCDD and OCDF as compared to all other transfer factors. For OCDD, it is also noteworthy that the total air concentration is 1 to 2 orders of magnitude higher than the concentrations for all other congeners.
3) The one congener whose air concentration is within an order of magnitude of OCDD is that of 1,2,3,4,6,7,8-HpCDD, at 0.116 pg/m3. Also, the calculated Bvpa for this congener is second in magnitude behind the OCDD/F congeners. Since 2% of this air concentration is, in fact, predicted to be in vapor phase according to the Bidleman model, vapor transfers are considered and the model predicted 21.0 ppt grass concentration, which compared favorably with the observed 30 ppt concentration.
4) Calibrations for some of the other congeners for which a discrepancy exists between hay/grass predictions and beef predictions were not attempted. However, one can see with the following how the trend between predicted grass to beef concentrations followed the observed grass to beef trend. That is, when the model underpredicted grass, it also underpredicted beef, and likewise for overpredicting:
grass/hay, ng/kg (ppt) whole beef, ng/kg (ppt)
Pred. Obs. Pred. Obs.
1,2,3,6,7,8-HxCDD 0.2 1.2 0.029 0.84
2,3,7,8-TCDF 7.1 ND* 0.46 0.06
1,2,3,4,6,7,8-HpCDF 1.4 5.4 0.04 0.40
*
the detection limits for hay sampling ranged from 0.30 to 6.5 ppt.5) A simple analysis of model performance indicates that vegetation concentrations explain beef concentrations. Looking only at 2,3,7,8-TCDD, it is seen that cattle soil ingestion, 4% of total diet, explains only 8.5% of final beef concentration, with grass explaining 60.6% and hay/silage/grain 30.9%. The main difference in grass and hay/silage/grain, as discussed above, is that vapor transfers are halved for hay/silage/grain with the use of the empirical VG parameter. Further, grass and hay/silage/grain concentrations are overwhelmingly dominated by vapor transfers for 2,3,7,8-TCDD, explaining 93% (grass) and 94% (hay/silage/grain) of final plant concentration. Since grass and hay/silage/grain explain over 90% of beef concentration, vapor transfers onto vegetations cattle consume are predicted to explain about 85% of final 2,3,7,8-TCDD beef concentrations in this exercise. Very similar predictions occur for all congeners, with the exception of OCDD/F where 100% was initially assumed to be in the particle phase. Allowing for the calibration described above, now the OCDD/F beef concentrations are dominated by vapor transfers. Further discussion of the importance of vapor-phase dioxins to vegetations and to beef/milk can be found in Section 6.3.3.11 in Chapter 6.
An air to soil examination begins with a comparison of predicted soil concentrations of the dioxin-like compounds and an observed concentration in soils, which is shown in Table 7-12. The observed data originated from four studies in the United States where soils were characterized as "rural" or "background". As seen in Table 7-13, there is clearly an underprediction trend for air to soil impacts. For the nine congeners where the literature allowed for a non-zero average soil concentration, the model appears to
Table 7-12. Comparison of concentrations of dioxin-like compounds found in soils described as "rural" or "background" with model predictions of soil concentrations.
Observed soil Predicted soil
Compound concentration, ng/kg1 concentrations, ng/kg
2378-TCDD 0.88 0.12
12378-PCDD ND 0.57
123478-HxCDD ND 0.56
123678-HxCDD 4.0 0.87
123789-HxCDD 9.0 1.17
1234678-HpCDD 194 13.9
OCDD 2372 69.3
2378-TCDF 1.59 0.8
12378-PCDF ND 0.7
23478-PCDF ND 0.5
123478-HxCDF ND 1.4
123678-HxCDF ND 1.3
123789-HxCDF ND 0.3
234678-HxCDF 2.0 1.0
1234678-HpCDF 47 4.9
1234789-HpCDF ND 0.7
OCDF 30.2 4.1
1
Observed data from Reed, et al. (1990), Pearson, et al. (1990), EPA (1985), and Birmingham (1990). Concentrations listed are the arithmetic mean of all observations available, counting non-detects as 1/2 detection limit. Only one study of the four noted had measurements for the eight congeners above with Non-Detects. This study, Reed, et al. (1990) listed soil detection limits as varying between 0.79 and 2.9 ppt, depending on site and congener.2
Geometric means were also determined for this data set. A wide range of concentrations of OCDD, ND to 10,600 ppt, led to a geometric mean of 60 ppt for this congener. For all other congeners, geometric means were within a factor of about 50% of arithmetic means.
underpredict soil concentrations by a range of about 2 to 10 times (i.e., observed concentrations are twice as high to about ten times higher than predicted concentrations). While this is a non-trivial result, in fact the model would not predict a substantially different beef concentration if soil concentrations were more in line with observations. If the soil concentrations were artificially increased by a factor of 10, than whole beef concentrations of total dioxins increase from 2.13 ppt to 3.62 ppt, and TEQ concentrations increase from 0.36 ppt to 0.45 ppt. The reason for this trend is that soil is only 4% of the beef cattle diet prior to feedlot fattening.
The observation made is that the current formulation and/or parameter assignments for an air to soil impact will underpredict soil concentrations of dioxins by about 2-10 times. If this observation is, in fact, a statement of truth, then the following is offered as the most likely causes for model underprediction:
1. The soil dissipation rate: The dissipation rate of 0.0693 yr-1, corresponding to a half-life of 10 years, was developed from field data of 2,3,7,8-TCDD applied to soils in the herbicide 2,4,5-T (Young, 1983). This may be appropriate for a limited loading onto a bounded area of soil. However, mechanisms for dissipation from this bounded area, such as dust suspension and volatilization, may not directly apply for background settings where such losses may be redeposited downwind. According to the steady state algorithm for soil impacts from depositions, the estimated soil concentration is an inverse function of the dissipation rate. If the dissipation rate is reduced to 0.00693 yr-1, corresponding to a half-life of 100 years, than the soil concentrations are increased by an order of magnitude.
2. Depositions of vapors: Koester and Hites (1992) developed the argument that their collection apparatus for dry deposition of dioxins would not scavenge vapor phase dioxins from the air; that they would only be measuring dry deposition of particle bound dioxins. Since the dry deposition velocities used in this paper originate from their work, and if their arguments are valid, then the algorithms of this paper do not consider the dry deposition of vapors. Their methods for measurement of wet deposition did not preclude the scavenging of vapors, although they do argue that rainfall is more effective at scavenging particle-bound dioxins compared to vapor-phase dioxins. Therefore, the assumption made that total annual wet deposition equals dry deposition made in this paper, based on the results of Koester and Hites, means that wet deposition of vapor phase dioxins are considered. In any case, algorithms to estimate the additional dry deposition loadings of vapor-phase dioxins to soil could not be found, so the impact of including them cannot be estimated.
3. Detritus recycling: This is another loading not considered, and also a loading tied directly to vapor-phase dioxins. As discussed above, vegetation concentrations are dominated by vapor transfers. Barbour, et al. (1980) list a detritus production rate for a setting described as "tallgrass prairie" as 520 g/m2-yr. Given the concentrations predicted to occur in grass, one can estimate the loadings of dioxin corresponding to a detritus production of this magnitude. This was done and compared against the estimated total deposition rates from the air to soil of individual congeners. It was found that detritus loadings varied by congener, and was equal to a range of 2% of atmospheric deposition to 100% (equal to) of deposition. Summing the depositions and the detritus loadings
of all congeners, it was found that detritus loadings are equal to about 20% of atmospheric deposition loadings of dioxins.
7.2.3.9.4. Conclusions
The beef bioconcentration algorithm of this assessment was tested in this section. A profile of air concentrations was crafted to be typical of rural environments where cattle are raised for production of beef. This profile was routed through the model to predict concentrations of dioxin-like compounds in beef. These predictions were compared with a profile of measured concentrations. An "observed" TEQ concentration of 0.48 ng/kg in whole beef was compared with a "predicted" 0.36 ng/kg. An observed total concentration PCDD/Fs of 8.15 ppt in beef was compared against the predicted 2.13 ppt. Further evaluations of the air to vegetation algorithm indicate the model appears to predict vegetation concentrations consistent with one set of literature observations, with the exception of the octa congeners, OCDD and OCDF. However, when assuming only a minute amount of the airborne reservoirs of these congeners is in the vapor phase, model predictions of both vegetations and subsequently beef concentrations fall in line. A final evaluation of the air to soil model indicates that the model and/or the parameter assignments tend to underpredict soil concentration by as much as an order of magnitude. Refinements to the model which would bring soil concentrations more in line with observations were offered. It was observed that while the model appears to be underpredicting soil concentrations, a more appropriate prediction would not change beef predictions significantly since soil is only a small part of the cattle diet. A major conclusion of this work is the overwhelming dominance of the vapor phase transfers to vegetations which cattle consume, which in turn implies that the appearance of these chemicals in beef and milk is due to vapor transfers.
Another and more broad conclusion offered is that the validation exercise in general demonstrates the validity of the air-to-beef model framework and parameter assignments. This is a cautious conclusion, obviously, given the uncertainty in the many parameter assignments and real world observations. This exercise would need refinement in several areas before ascribing any finality to the model structure and results. Following is a summary of the key uncertainties of this exercise:
1. A characteristic rural air environment: A profile of air concentrations of dioxin-like congeners in a rural environment in the United States could not be found for this exercise, and instead one was crafted given a representative profile for urban/suburban areas and a simple proportional reduction.
2. A characteristic profile of dioxin-like congeners in beef: Only 14 samples from three literature references, one of which only reported on 2,3,7,8-TCDD and 2,3,7,8-TCDF, were found for this exercise.
3. Vapor/particle partitioning: A theoretical modeling approach was used to partition the total reservoir of congeners into particle and vapor phase. A carefully designed monitoring experiment could shed some light on vapor/particle partitioning for dioxin-like compounds. This is obviously critical given the major conclusion of the dominance of vapor phase concentrations in explaining beef concentrations.
4. Vapor transfers to vegetations: Like the partitioning issue, the quantification of transfers onto vegetations is critical. The generalized model of Bacci (1990, 1992) was used with an empirical refinement suggested by McCrady and Maggard (1993). To highlight the importance of this empirical reduction, consider the following which describes what predictions would be without the benefit of the McCrady adjustments. A factor of 40 difference was noted in the measured transfer of 2,3,7,8-TCDD, on a volumetric basis, to grass leaves in the McCrady experiments compared to the transfer which would be estimated using the empirical algorithm developed by Bacci and coworkers. This factor of 40 was applied to the transfer factor of all dioxin-like compounds. The volumetric transfer factor was transformed to a mass-based transfer factor using plant densities and percent dry matter suggested by McCrady rather than those used by Bacci and coworkers for the azalea leaf. Together, the final mass-based Bvpa of this exercise, and this assessment otherwise, is about a factor of 20 lower than that which would be estimated using the Bacci mass-based algorithm. Said another way, the model would have predicted a whole beef concentration greater than 7 ppt, instead of 0.36 ppt. Also, a second empirical refinement reduced the transfer into bulky vegetations. While the need for both refinements is argued to be justified for dioxin-like compounds, the precise numerical adjustments used in the exercises above cannot be rigorously defended without further data.
5. Particle depositions onto vegetations: The impact of wet deposition needs to be further investigated. A literature article suggesting that about 30% of particles depositing in rain are retained on the canopy after the rainfall justified the assignment of 0.30 to the parameter, Rw (fraction retained on vegetation from wet deposition). The weathering half-life of 14 days, while often used for dioxins, is also identified as uncertain. Finally, the deposition velocity of 0.2 cm/sec should be considered further.
6. Air-to-soil impacts: The trend here is that the model appears to underpredict soil concentrations by an order of magnitude or less. Three aspects of the model were offered above as possible candidates for refinement and further research. These included: vapor impacts to soils, dissipation rate in soils, and detritus loadings to soils.
7. The bioconcentration factor: Only one study was found from which congener-specific bioconcentration factors for the suite of congeners could be developed, and this was for one cow, for one lactating period, and was for milk and not beef. The differences in bioconcentration between beef and milk need to be further investigated and quantified.
8. Cattle diet and the impact of feedlot fattening: A cattle diet was simplistically assumed to consist of 4% soil and equal parts of grass and non-grass feeds. Perhaps a more representative diet could be crafted, which would lead to a different exposure pattern by the beef cow prior to feedlot fattening. Equally if not more important is the impact of this feedlot fattening. It is clear that commercial beef cattle in the United States undergo a period of feedlot fattening. However, before and after monitoring quantifying the impact of this practice could not be found. Two modeling studies, which assumed that dilution and depuration were occurring during feedlot fattening, estimated that concentrations were halved due to this process. This was the assumption also made in this paper, and it needs to be further evaluated.
7.2.3.10. Comparison of modeled beef and milk concentrations with concentrations found
The example scenario in Chapter 5 demonstrating the on-site source category (where the soil at the place of residence/farming/exposure is the source of contamination) had soil concentrations initialized at 1 ng/kg (ppt) 2,3,7,8-TCDD. This concentration was chosen because it was similar to concentrations of 2,3,7,8-TCDD found in studies where researchers had measured what they characterized as "rural" or "background" soils. Beef and milk fat concentrations of 2,3,7,8-TCDD estimated with this soil concentration were 0.12 and 0.06 ppt 2,3,7,8-TCDD, respectively. Assuming fat contents for beef and milk of 0.22 and 0.035, respectively, whole beef and milk concentrations are estimated as 0.03 and 0.002 ppt. Beef and milk fat concentrations for an exposure site located 500 meters from a hypothetical incinerator, another of the example scenarios in Chapter 9, were 0.0024 and 0.0017 ppt. Corresponding whole beef and milk concentrations were 0.0005 and 0.00006 ppt. The other source category was a site of higher soil concentration located near a site of exposure. It was termed the off-site source category, and the demonstration scenario had a 4 hectare site contaminated with 2,3,7,8-TCDD at 1 m g/kg (ppb) located 150 meters from an exposure site. This concentration was selected based on similar 2,3,7,8-TCDD concentrations found in sites of elevated contamination, such as Superfund sites. No-till soil concentrations at the site of exposure, the concentrations which beef and dairy cattle were exposed to, were estimated to be 0.28 ppb, or 280 ppt. Concentrations in beef and milk fat were 38 and 19 ppt, respectively, which corresponds to whole product concentrations of 17 and 0.7 ppt.
A limited number of studies were available to estimate concentrations of dioxin-like compounds in beef suitable for background exposure estimations. Data from these studies is summarized in the previous section, Section 7.2.3.9. From this limited data, the concentration of 2,3,7,8-TCDD in beef/veal fat was estimated at 0.134 ppt when non-detects were assumed to equal one-half the detection limit and 0.060 ppt when non-detects were assumed equal to 0.0. A single report containing milk concentrations (Lafleur, et al., 1990) indicated a concentration of 0.054 ppt in milk fat. This compares to the 0.12 ppt estimated for beef fat and 0.06 ppt estimated for milk fat for the demonstration scenario based on a background soil concentration of 1 ppt.
The example scenario results from the stack emission source estimated beef and milk concentrations over a factor of ten lower than for the background soil concentration scenarios. In interpreting this result, it is important to note that the emission rates assumed in this example scenario were characterized as typical of incinerators with a high level of air pollution control, e.g., scrubbers with fabric filters. The TEQ emission factor (mass TEQs emitted per mass feed material combusted) for the demonstration scenario was 4.5 ng/kg, which was compared to a crafted range of 0.3 ng/kg (for a municipal solid waste incinerator) to 200 ng/kg (for a medical waste incinerator) which had similar high levels of air pollution control. Also, the 200 metric tons per day feed material assumed for the example scenario is considered midrange (see Chapter 3 for more details). Some articles in the public literature suggest a greater impact to milk when the milk is produced near incinerators or urban centers, although a direct comparison obviously is not warranted without a careful evaluation of source strengths from these literature articles, which is not done here. A study sampling remote farms in England also sampled two farms near incinerators and two farms near industrial centers. Whereas samples from remote farms averaged 0.009 ppt for whole milk, two concentrations near the incinerators were 0.034 and 0.036 ppt 2,3,7,8-TCDD, and the samples near the industrial centers were 0.043 and 0.081 ppt (Startin, et al., 1990). A study from Switzerland which sampled milk from locations remote from 2,3,7,8-TCDD sources, and did not find detectable residues, also sampled three locations that were within 1000 meters of incinerators (Rappe, et al., 1987). Whole milk concentrations near the incinerators were 0.021, 0.038, and 0.049 ppt.
Sampling of beef and milk near areas of elevated soil concentrations, or where cattle were raised on soils with known high concentrations of 2,3,7,8-TCDD, were not found in the literature. Therefore, the beef fat concentration of 38 ppt (whole beef equal to 8 ppt) estimated to occur near an area where soil concentrations of 2,3,7,8-TCDD were 1 ppb cannot easily be evaluated. There are some studies on other animals indicating high tissue concentrations in areas of high soil contamination of 2,3,7,8-TCDD. Lower, et al. (1989) studied animal tissues for wild animals in the abandoned town of Times Beach, Missouri, and compared their results for similar wild animals tissue concentrations found in Eglin Air Force Base in Florida; Seveso, Italy; and Volgermeerpolder, Holland. With 2,3,7,8-TCDD soil levels in these areas in the hundreds to thousands of ppt, tissue levels for earthworm, mouse, prairie vole, rabbit, snake, and liver samples from some of these animals, were in the tens to thousands of ppt.
There is an episode of beef and dairy cows being raised on lots where the soil was heavily contaminated with polybrominated biphenyls (PBB; details can be found in Fries and Jacobs, 1986; and Fries, 1985). Soil concentrations to which dairy and beef cows were exposed were 830 and 350 m g/kg (ppb), respectively. Body fat of the dairy cows had PBB concentrations of 305, 222, and 79 ppt (dairy heifers, primiparous dairy, and multiparous dairy, respectively). Body fat for the beef cows exposed to 350 ppb soil levels were 95 (cows) and 137 ppt (calves). Milk fat concentrations from the primiparous dairy and multiparous dairy cows exposed to 830 ppb soil levels were 48 and 18 ppt.
Fries estimated a quantity which is also useful for purposes of comparison - this quantity is the ratio of concentration in animal fat to concentration in soil to which the animal is exposed. His justification for deriving this ratio is that soil was speculated as the principal source of body burdens of PBB in the data listed above. For the source categories where contaminated soil is the source of dioxin-like compounds, the on-site and off-site source categories, a similar assumption is warranted. Ratios he derived for body fat of dairy heifers ranged from 0.10 to 0.37, while it was 0.02 and 0.06 for milk fat. For body fat of beef cows, these ratios were 0.27 and 0.39. Fries also measured a ratio of 1.86 for sows and gilts. He attributes much higher sow ratios to their tendencies to ingest more soil. Analogous ratios can be derived for the contaminated soil source categories, and for beef and milk fat. For the onsite source category with low soil concentrations, beef fat to soil and milk fat to soil ratios were 0.12 and 0.06, respectively. For the off-site source category, ratios were similar at 0.14 for beef fat and 0.07 for milk fat. The milk fat ratios compare favorably with PBB ratios derived by Fries (1985), although the beef fat ratios appear generally lower.
This is, once again, some indirect evidence that the soil to air models may be underestimating air concentrations. This had been discussed earlier in Section 7.2.3.7 on air concentrations and 7.2.3.8. on soil to plant relationships. For the current discussion, a higher beef fat:soil ratio would result if air concentrations were increased and hence the cattle vegetation concentrations would increase.
7.2.4. Alternate Modeling Approaches for Estimating Environmental and Exposure Media Concentrations
This section examines alternate modeling approaches for estimating environmental and exposure media concentrations. This is by no means a comprehensive examination, nor is its purpose to justify the models selected. If the models examined can be shown to be similar or to arrive at similar results as the models of this assessment, perhaps some validity for modeling and/or the models selected for this assessment can be gained.
7.2.4.1. An alternate approach for estimating bottom sediment concentrations from watershed soil concentrations
The dilution of contaminated sediments entering a river system can be estimated using an alternate approach. The average runoff rate for the midwestern U.S. is about 15 inches/year (Linsley, et al., 1982), the value used in this assessment for determining the flow rate of the receiving water body. For a 10,000-acre watershed (4,000 hectares; the watershed size and effective drainage area for the example scenarios in Chapter 5), this yielded a stream flow of about 17.2 ft3/sec. The sediment yield can be estimated from the stream flow as follows (Linsley, et al., 1982): Qs = aQn, where Qs = sediment flow rate (Eng. T/yr); Q = stream flow rate (ft3/sec); and a and n are empirical constants, reflecting the vegetative cover in the watershed. Linsley, et al., (1982) recommend using a=3,500 and n=0.82 for coniferous forest and tall grass, and a=19,000 and n=0.65 for scrub and short grass. Substituting these into the equation above (and Q = 17.2 ft3/sec) gives an annual sediment flow rate of 36,000 to 121,000 T/yr. Annual sediment flows will be assumed to consist only of soils which have eroded during the year. As such, sediments will be comprised of contaminated as well as uncontaminated watershed soils. A "contaminant concentration ratio" can be calculated by estimating the sediment contributed by the contaminated areas and dividing by this sediment flow rate range; this assumes all other sediment contributions are uncontaminated. The annual soil loss for Scenario 3 demonstrating the off-site scenario was 9.6 T/ac-yr. The contaminated site area for Scenario 3 was 10 acres (4 ha). The total soil erosion contributed by this site equals: the unit soil loss * area * soil delivery ratio; for Scenario 3, this equals 9.6*10*0.26, or 25 T/yr. The contaminant concentration ratio is (25 T/yr)/(36,000 to 121,000 T/yr), or a range of 0.0002-0.0007.
This can be compared to a contaminant ratio estimated using current methodologies. The example Scenario 3 which had soil concentrations at 1 ppb resulted in a bottom sediment concentration in the nearby water body of 0.0016 ppb, which leads to a contaminant concentration ratio of 0.0016. This is higher than the ratio range noted above. It does incorporate an "enrichment ratio", however, which is the ratio of contaminant concentration on soils eroding from a field to soils within the field. It is given a value of 3 for the demonstration scenario. The ratio range noted above did not consider enrichment; if it had, the range would instead by 0.0006-0.0021. Now the modeled 0.0016 and this range are comparable.
7.2.4.2. An alternate modeling approach for estimating water concentrations given a steady input load from overland sources
A study to evaluate the bioaccumulation of 2,3,7,8-TCDD in fish in Lake Ontario included an extensive modeling exercise (EPA, 1990a). The model used was WASP4 (Ambrose, et al., 1988). This is a substantially more complicated model than used in this assessment. The underlying principal for the WASP4 model is a conservation of mass. Contaminant source terms, described in mass/time units, enter what are termed control volumes, or segments. The contaminant partitions between sorbed, bound, and dissolved phases; it is not required to specify whether the contaminant enters via soil erosion, water runoff, surface deposition, or otherwise. Contaminants are, however, assumed to enter via the surface or as part of inflows to the water body, in contrast to ground water recharge. The mass transported into a segment is either transported out of the segment, accumulates in the segment, or is transformed by chemical or biological reactions.
As noted, 2,3,7,8-TCDD input into the Lake Ontario application partitions within the water column into a sorbed compartment, a dissolved compartment, and a bound compartment. This bound compartment is further described as non-settling organic matter. Three analogous compartments receive 2,3,7,8-TCDD in the bottom sediment layer. Several exchanges between the six compartments and contaminant losses within each compartment are modeled. For example, losses from water column compartments include downstream transport, volatilization and photolysis; the loss mechanism from the bottom sediment layer is sedimentation. Exchanges between compartments consider partitioning, diffusion, and sediment settling and resuspension.
This model requires substantial parameterization. Once values were selected for the Lake Ontario application, an evaluation was made on the impact of different levels of 2,3,7,8-TCDD input. Dynamic and steady state results were discussed. Principally examined for the steady state results were the concentrations of bottom sediment sorbed 2,3,7,8-TCDD and water column dissolved (soluble) phase 2,3,7,8-TCDD. A given level of steady 2,3,7,8-TCDD input, in kg/yr, resulted in a steady state concentration sorbed to bottom sediment and dissolved in the water column.
The premise in both the Lake Ontario steady state application of WASP4 and the water concentration algorithms in this assessment is that contaminants continue to enter water bodies over time unabated. Ground water entry of contaminants is not considered in either approach. Although a direct modeling comparison cannot be done, it is possible to slightly adjust the algorithms of this assessment to evaluate how results from a simple partitioning approach would compare with results from the complex fate and transport approach of the WASP4 steady state application.
Assume a surface water body is initially free of contaminant and at time t equals 1 day, a strongly hydrophobic contaminant, such as the dioxin-like compounds of this assessment, begins to enter a lake. Assuming the contaminant enters via soil particles, as in the approach of this assessment, it will then partition between those soil particles and surrounding water. The soil particles will slowly move toward the bottom of the lake at a rate described by a particle settling velocity. A settling velocity of 1 m/day is assumed in the Lake Ontario simulations. The amount of time it takes to settle to the bottom once entering from the surface equals the lake depth divided by this settling time. The Lake Ontario depth was 86 m. Therefore, it might take 86 days to settle. This, of course, neglects resuspension of settled particulates. With this simplistic framework, a steady state amount coming into the lake after 86 days is matched by an amount depositing onto the lake bottom; the amount of contaminant within the water column has reached steady state. Water concentrations can then be estimated assuming equilibrium partitioning.
Results of sediment and water column steady state concentrations are described for any loading of 2,3,7,8-TCDD in the WASP4 steady state application; those loadings are described in kg/yr. Loadings in kg/yr are easily correlated to a steady state water column amount, given the above analysis. For example, a loading of 1.0 kg/yr could translate to a within water column steady state amount of 0.24 kg (1.0 kg/yr * (86 d)/(365 d/yr)).
This steady water column amount partitions between suspended sediment and surrounding water. First, the total concentration (sorbed + soluble) simply equals:
where:
Ctot = total concentration, mg/L
LD = water column steady state amount of contaminant, kg
VOL = lake volume, m3
1000 = converts kg to mg and m3 to L
The dissolved phase portion of total is given by:
where:
Cwat = soluble phase water concentration, mg/L
Ctot = total concentration, mg/L
Kdssed = partition coefficient between suspended sediment and surrounding water, L/kg
= Koc*OCssed
Koc = organic carbon partition coefficient, L/kg
OCssed = fraction organic carbon of suspended sediments
TSS = total suspended sediments, mg/L
10-6 = converts mg/kg to mg/mg
Parameters in this equation for the Lake Ontario WASP4 application include VOL, Koc, OCssed, and TSS. Lake Ontario volume was given as 1.68 x 1012 m3, Koc was estimated for the WASP4 application as 3,162,000, OCssed was estimated at 0.03, and TSS was estimated 1.2 mg/L. For a steady load of 1 kg/yr and a resulting LD of 0.24 kg, the steady state water column 2,3,7,8-TCDD concentration, using the simplistic approach described above, is estimated as 0.13 pg/L (ppq). The steady state water column concentration estimated by WASP4 given the same parameters and a load of 1 kg/yr is roughly 0.20 pg/L. An uncertainty analysis done with these WASP4 results concluded
that 95% confidence limits around this prediction are 0.03 and 0.40 pg/L.
This would seem to imply that the simple partitioning approach used in this assessment compares favorably with the more complex fate and transport modeling assessment using WASP4, for Lake Ontario.
7.2.4.3. Estimating fish tissue concentrations based on water column concentrations rather than bottom sediment concentrations
EPA has prepared a document titled, "Interim Report on Data and Methods for Assessment of 2,3,7,8-Tetrachlorodibenzo-p-Dioxin Risks to Aquatic Life and Associated Wildlife" (EPA, 1993). That document provides details on the two key bioaccumulation parameters used for the methodologies of this document, the Biota Sediment Accumulation Factor, BSAF, used for the soil and stack emission source categories, and the Biota Suspended Solids Accumulation Factor, BSSAF, used for the effluent discharge source category. That document also discussed several water column based bioaccumulation factors, which are the focus of this section.
Before discussing these factors, it is noted that food chain modeling is a well developed alternate approach for estimating fish tissue concentrations of bioaccumulating contaminants (Thomann, 1989), which has also been applied to 2,3,7,8-TCDD (Parkerton, 1991). This approach is significantly more complex than the bioaccumulation/biotransfer approach of this methodology. It involves detailed site-specific characterizations, specifically the identification and transfer modeling between trophic levels of a food chain in a water body. Food chain modeling is a mechanistic approach, while the transfer approaches of this methodology are empirical. No judgement is rendered as to the relative merit of food chain models versus use of bioaccumulation coefficients. If detailed site-specific data is available, and given time and resources, assessors should consider food chain modeling for estimating fish tissue concentrations.
One water column measure which has been classically used is termed the Bioconcentration Factor, or BCF. Bioconcentration refers to the net accumulation of a chemical from exposure via water only, and BCFs are most often obtained in laboratory conditions. BCFs are defined as the ratio of the chemical concentration in organism (mass of chemical divided by wet weight of organism tissue) to that in water.
Another water column measure of the potential for a contaminant to accumulate in fish tissue is termed the Bioaccumulation Factor, or BAF. Bioaccumulation refers to the net accumulation of a chemical from exposure via food and sediments as well as water. Similar to the BCF, BAFs are defined as the ratio of the chemical concentration in the organism to that in the water.
For chemicals that are not strongly hydrophobic (unlike the dioxin-like compounds), the distinction between bioconcentration and bioaccumulation is small. Whereas food intake is generally a few percent of body weight per day, water passing over gills will equal hundreds to thousands times the organism weight per day, depending on species, activity, temperature, and other factors. Given this, the concentration of chemical in food must be 3 or more orders of magnitude greater than that in water before food can substantially contribute to uptake. EPA (1993) estimates that food intake becomes a critical contributor to the accumulation of contaminants in fish tissue for contaminants with log Kow of 5 and greater.
Since the dioxin-like compounds fall into this category, the remainder of this section will focus on the Bioaccumulation Factor. EPA (1993) defines steady-state lipid-based BAFs for total chemical in water and freely dissolved chemical in water (i.e., chemical which is truly in a dissolved phase and not bound to dissolved or suspended particulate organic materials) as:
where:
ssBAFlt = steady-state lipid-based BAF for total chemical in water, unitless
Clipid = the mass of contaminant in fish lipid tissue divided by the mass of fish lipid tissue, mg/kg
Cwt = the mass of total contaminant in water divided by the mass of water in the water body, mg/kg (note: 1 L water nearly equals 1 kg, therefore, 1 mg/L can be assumed to equal 1 mg/kg)
ssBAFld = steady-state lipid-based BAF for freely dissolved chemical in water, unitless
Cwd = the mass of freely dissolved contaminant in water divided by the mass of water in the water body, mg/kg
EPA (1993) then develops relationships between ssBAFld and ssBAFlt, based on dissolved and particulate organic carbon reservoirs in the water column, and partition coefficients for these reservoirs. This is meaningful in complex modeling where these two reservoirs of organic carbon can be accounted for, such as in the WASP4 model. Alternately, EPA (1993) defines the TBFoc, a total binding factor to organic carbon, which empirically considers the reservoir of dissolved organic material (i.e., increases total binding and reduces truly dissolved phase concentrations) when such a reservoir is not explicitly modeled. The modeling frameworks in this assessment have only one compartment of suspended material to which contaminants sorb, with one associated organic carbon content. A second reservoir to which contaminants bind, the reservoir of dissolved organic material, is not modeled.
EPA (1993) developed a ssBAFlt and a ssBAFld for lake trout, 2,3,7,8-TCDD, and for Lake Ontario 1987 contamination conditions. The WASP4 model was used to model three hypothetical loading conditions that might have resulted in fish tissue concentrations observed in 1987: steady state loading, a steady state loading followed by a 90% reduction in annual loads for 20 years (i.e., 1968-1987), a steady state loading followed by a 100% reduction (i.e., no loading) for 20 years. The BSAF for lake trout estimated for 1987 data is given in EPA (1990a) as 0.07. The BSAF is determined from measured bottom sediment concentrations and fish tissue concentrations; an assumption of historical loading is not necessary for BSAF development. Details of the Lake Ontario study, including initial modeling efforts with the WASP4 model can be found in EPA (1990a). Slight refinements to the WASP4 runs were later made (cited in EPA, 1993 as an unpublished report: Endicott, D.D., W.L. Richardson, T.F. Parkerton, and D.M. DiToro. 1990. A steady-state mass balance and bioaccumulation model for toxic chemicals in Lake Ontario: Report to the Lake Ontario Fate of Toxics Committee. U.S. EPA, Environmental Research Laboratory, Duluth, MN: 121 pp). The BAFs determined in these later runs will be tested using the models of this assessment.
In order to do this exercise, all critical model parameters used to develop the BAFs for this WASP4 modeling exercise will be used in the model framework of this assessment. The most critical parameter is the organic carbon partition coefficients, Koc, assumed for 2,3,7,8-TCDD. BAFs were determined assuming Koc of 107 and 108. Since the models of this assessment assume steady loading into water bodies, only the BAFs developed under "steady state" loading conditions will be used. As noted, the WASP4 model considers binding to more than one suspended compartment. The increased binding can be modeled using a TBFoc, which was assumed to be 1.5 for Lake Ontario by Cook. For the models of this assessment, this factor will be applied to Koc - it effectively increases Koc by 50%. The concentration of suspended solids in Lake Ontario and used in the WASP4 modeling exercise was 1.2 mg/L. The other critical parameters are the fraction organic carbon contents of the suspended solids and the bottom sediments, OCssed and OCsed, respectively. Assigned values to these parameters, based on Lake Ontario data, in the WASP4 exercise and in this exercise were 0.15 (15%) and 0.03 (3%), respectively.
Since the purpose of this exercise is to evaluate how the modeling approaches of this document perform using the BSAF or the alternate BAF approach, duplicating the source strength terms used in the WASP4 modeling exercise is not necessary. The pertinent question is, with a given source strength, how would both approaches predict fish tissue concentrations. For simplicity, the on-site source category as demonstrated in Chapter 5 will be used. In this scenario, the soil within the watershed is assumed to uniformly be 1.0 ppt, and the loadings are via soil erosion.
In summary, the parameters for this exercise including the steady state BAFs are:
Test 1: Koc = 1.5*107; ssBAFld = 1.9x106; ssBAFlt = 5.16x105; BSAF = 0.07
Test 2: Koc = 1.5*108; ssBAFld = 1.9x107; ssBAFlt = 6.78x105; BSAF = 0.07
The 1.5 in the Kocs was the TBFoc noted above. The BAFs specific to each Koc were the ones developed also specific to those Koc in the WASP4 modeling exercises. For both tests: soil concentration of 2,3,7,8-TCDD = 1.0 ng/kg (ppt), total suspended solids (TSS) = 1.2 mg/L, the organic carbon content of suspended sediments (OCssed) = 0.15, and the organic carbon content of bottom sediments (OCsed) = 0.03. Whole fish tissue concentrations are estimated as Clipid * flipid, where flipid is 0.07.
The whole fish tissue concentration for the BSAF approach in Test 1 was estimated to be 0.61 ppt. Using the ssBAFlt and ssBAFld, the whole fish tissue concentrations were estimated very nearly to be the same at 0.867 ppt for ssBAFlt and 0.863 ppt for ssBAFld. The test results did not change substantially for Test 2. The BSAF approach led to a fish tissue concentration of 0.62 ppt, and the concentration was identical for BAFs at 0.869 ppt.
While it appears that the water column based approaches estimate fish tissue concentrations identical to each other and very close to estimates made based on bottom sediment concentrations, in fact the performance of the models differ when parameters are changed in these tests. More incoming 2,3,7,8-TCDD can be modeled to remain in the water column with an increase in the reservoir of total suspended solids, the TSS parameter initialized in above tests at 1.2 mg/L. Continuing with Test 1 parameters above, increasing TSS from 1.2 mg/L to 10 mg/L has the following changes to fish tissue concentrations: 0.54 ppt for the BSAF test, 4.85 ppt for the ssBAFlt test and 0.76 ppt for the ssBAFld test. Decreasing the organic carbon content of the suspended solids will have the effect of reducing the amount of incoming 2,3,7,8-TCDD simulated to remain in the water column, while increasing the amount modeled to reside in bottom sediments (because a mass balance of 2,3,7,8-TCDD is maintained), and also increases the dissolved phase concentration. Changing the TSS back to 1.2 mg/L and reducing the organic carbon content of suspended solids from 0.15 to 0.05 results in the following changes to fish concentrations: 0.62 ppt for the BSAF test, 0.45 ppt for the ssBAFlt test and 0.88 ppt for the ssBAFld test. These two tests have demonstrated the variability in fish tissue concentrations when key water column parameters are altered. Fish concentrations would also differ if the key bottom sediment parameter, the organic carbon content of bottom sediments, was different. Returning to original Test 1 parameters and reducing the organic carbon content of bottom sediments from 0.03 to 0.01 results in the following changes to fish concentrations: 1.73 ppt for the BSAF test, 2.45 ppt for the ssBAFlt test and 2.44 ppt for the ssBAFld test.
The predictions for all tests might be considered reasonably close, given the uncertainties in the bioaccumulation and water modeling parameters. The one test described above where the BSAF and BAF approaches led to the most differences was the one which increased suspended material contents from 1.2 mg/L to 10 mg/L. In that case, nearly a ten-fold difference was noted in fish concentrations with the ssBAFlt as compared to the BSAF or the ssBAFld.
An important consideration in using the water column based approaches is that the BAFs developed by Cook (or that could be developed otherwise) are based on modeled rather than measured water column concentrations, and measured lake trout tissue concentrations. In that sense, the BAFs were calibrated for Lake Ontario conditions and specific to the WASP4 modeling exercise. Therefore, using these BAFs in the modeling framework of this assessment is, strictly speaking, invalid. Further, the values of the BAFs varied depending on the assumptions on historical loadings into Lake Ontario. As noted above, three loading conditions were tested. The steady state BAFs were given above. For the 20 year - 90% reduction tests, the following BAFs were determined: BAFld was 3.03x106 for Koc = 107 and 2.86x107 for Koc = 108, and BAFlt was 8.26x105 for Koc = 107 and 1.02x106 for Koc = 108. For the 20 year - 100% reduction tests, the following BAFs were determined: BAFld was 3.86x106 for Koc = 107 and 3.40x107 for Koc = 108, and BAFlt was 1.05x106 for Koc = 107 and 1.21x106 for Koc = 108. The BSAF developed for lake trout for Lake Ontario was developed using measurements of both fish tissue and bottom sediment concentrations.
Both the BSAF and BAF are most appropriately developed using site specific data (coupled with a modeling exercise for BAF). Inasmuch as that can be impractical or difficult for many sites, efforts are underway to determine the general applicability of BSAFs and BAFs determined for one site to other sites. EPA (1993) proposes that BAFls for different congeners can be roughly estimated as the BAFl for 2,3,7,8-TCDD multiplied by the ratio of the BSAF for the congener and the BSAF for 2,3,7,8-TCDD. Such an estimate will incorporate differences in uptake, metabolism and chemical partitioning but not differences caused by chemical loss processes such as volatilization and photolysis. This approach for estimating BAFls for other congeners does allow for some generality since sediment and fish tissue data for other congeners and water bodies is available.
Another bioaccumulation term discussed in one literature article for dioxin is termed the Regulatory Bioaccumulation Multiplier, or RBM (Sherman, et al., 1992). Multiplication of this term and a "nominal water concentration" estimates a 3% lipid fish concentration. A nominal water concentration equals an amount of a contaminant, 2,3,7,8-TCDD in this application, added or entering a water body over time, divided by a flow volume over that same time. Assuming a fish lipid content of 3%, an RBM of 5000 was recommended based on examination of laboratory flow through data, simulated field data, and actual field data (EPA's Lake Ontario study and data downstream of pulp and paper mills). Dividing the 5000 by 0.03 gives 1.67*105, and this number is now analogous to the ssBAFlt developed by EPA (1993) described above, and in the same range as the 5.2-6.8*105 range for ssBAFlt.
7.2.4.4. Other modeling approaches and considerations for air concentrations resulting from soil volatilization
Volatilization flux was modeled using an approach given in Hwang, et al. (1986), developed for PCB flux from soils. Principal assumptions for their derivation were that contamination extended indefinitely, biodegradation or other degradation processes were not considered, residues were in equilibrium between soil and soil air, and vertical movement was through vapor phase diffusion. Their analytical solution was integrated over time and a solution was presented which gave average unit flux as a function of time during which volatilization occurs. PCBs and other dioxin-like compounds resist degradation, although there is evidence of photodegradation, which may influence surficial residues. These compounds sorb tightly to soil, so that an assumption of vertical movement primarily through vapor phase diffusion (rather than in a soluble phase with leaching, runoff, or evaporating water) is a tenable one. Also, presentation of an average flux rate solution made Hwang's approach amenable to spreadsheet analysis, the computer software tool used in this assessment.
An alternate model for estimating volatilization flux was presented in Jury, et al. (1983). It is a generalized analytical solution which assumes equilibrium between the sorbed, soluble, and vapor phases. It incorporates considerations of steady state water fluxes and degradation mechanisms. A depth over which contamination occurs is specified. A computer code of this model was obtained from the author (William A. Jury, Professor and Chair, Department of Soil and Environmental Sciences, University of California, Riverside, 92521-0424). Tests were run holding all pertinent quantities the same with both models including initial concentrations, organic carbon partition coefficients, Henry's Constant, molecular diffusivity, fraction organic carbon in soil, soil bulk density, porosity, and an assumption of contaminant non-degradation. All of these parameters, the contaminant as well as the physical parameters, were the ones assumed for 2,3,7,8-TCDD and the surface soils of this assessment. In applying Jury's model, the depth of contamination was assumed to be 10 cm. Also, Jury's model allowed for a selection of water flux to be 0.5 cm/day (heavy leaching), -0.5 cm/day (heavy evapotranspiration), or 0.0 cm/day (no water flux). The latter selection of no water flux was chosen. This model comparison test showed that the Hwang model predicted an average flux over 10 years roughly three times higher than the average flux predicted by the Jury model over the same time period. Running both models over 50 years showed similar results. The average flux over that time dropped by about 50% for both models and there was still a three-fold difference in predicted volatilization fluxes. The exact reason for this three-fold difference was not investigated, and could lie in differences in assumed boundary conditions (Hwang, et al. (1986) discusses differences in boundary conditions between his and Jury's models). In any case, it is judged that both models predict comparable volatilization fluxes. The Hwang model might be considered conservative in that it predicts 3 times higher volatilization flux (with 2,3,7,8-TCDD parameters, etc.).
The Jury model also provides other informative results. It provides a mass balance which, for the 50-year test, showed that only 2.6% percent of the original mass within the 10-cm layer had volatilized. By implication, the Hwang model predicts a 7.3% loss by volatilization over that time period. With the other parameters and assumptions - no degradati