169 A PPENDICES L1401-frame-A1 Page 169 Monday, April 10, 2000 10:23 AM © 2000 by CRC Press LLC 171 A PPENDIX A1 Symbols Used in Systems Diagrams (a) Producer (b)Consumer (c) Miscellaneous Box (g) Storage (h) Interaction (Production) (i) Switch (j) Amplifier (l) Exchange (f) Heat Sink(d) Source (k) Adding & Splitting (e) Defined Boundary $ L1401-frame-A1 Page 171 Monday, April 10, 2000 10:23 AM © 2000 by CRC Press LLC 173 A PPENDIX A4 Biogeochemical Cycle of Lead and the Energy Hierarchy Howard T. Odum Table A4.1 Global Storages of Lead Note Item E10 Grams 1 Seawater recently 2.74 E3 2 Seawater originally 21.9 3 Atmosphere now 1.84 4 Atmosphere originally 0.28 5 Soil, glaciers 4.8 E5 6 Deltas, wetlands, sediments 4.8 E9 7 Land 3.2 E9 8 Ore 1.4 E4 9 Civilization 3.47 E4 Notes: 1, 3, 5, 6. Nriagu (1978, page 10). 2. Use concentration in the deep sea as representative: 0.02 µ g/kg (from Chow and Patterson, 1966). (2 E-5 g/m 3 )(1.37 E9 m 3 seawater) = 2.7 E4 g. 4. In original air 5.3 E-10 g/m 3 surface air (from Patter- son, 1965). (5.3 E-10 g/m 3 )(1 E-3 m 3 /g surface air)(5.2 E21 g atmosphere) = 0.28 E10 g. 7. Lead is 16 ppm in rock (Bowen, 1979) 2.2 E24 g. Uplifted continental sediments: (16 E-6 g/g rock)(2.2 E24 g) = 3.15 E19 g. 8. Lead reserves 141 E6 short tons (Kesler, 1978). (141 E6)(0.907) = 128 E6 tonne = 1.28 E14 g. 9. Civilization storage, order of magnitude estimate: Net production rate in Figure 4.6 (4000–534 E9 g/year)(100 years) = 3.47 E14 g. L1401-frame-A4 Page 173 Monday, April 10, 2000 10:25 AM © 2000 by CRC Press LLC 174 HEAVY METALS IN THE ENVIRONMENT: USING WETLANDS FOR THEIR REMOVAL Table A4.2 Global Flows of Lead in Figure 4.6 Note Item E9 Grams/Year 1 Seawater to sediments 2.5 2 Seawater to atmosphere 2 E-5 3 Atmosphere to seawater 210 4 Atmosphere to ecosystems 320 5 Ecosystems runoff to deltas 720 6 Predevelopment runoff 180 7 Deltas to open seawaters 34 8 Deltas and sediments to deep earth ? 9 Deltas, sediments to land 94 10 Sedimentary land to ecosystems 400 11 Normal weathering to ecosystems 18 12 Deep earth to land ? 13 Continental land to ores ? 14 Ores to economy 4000 15 Deep earth to ores ? 16 Economy to atmosphere 440 17 Economy via rivers to sediments 60 18 Economy solids to land 34 19 Volcanoes to atmosphere 0.4 20 Land to atmosphere 5.9 21 Land dust and organics to atmosphere 32 Notes: 1–5, 8, 10, 12–19, 21. Nriagu (1978). 6. River runoff before wastes: 180 E9 g/year (from Bowen, 1966). Natural denudation 1.1 E10 g/year (Tatsumoto and Patter- son, 1963). 7. To open sea 34 E9 g/year (after Tatsumoto and Patterson, 1968 quoted by Chow, 1978). 9. Land cycle: (2.4 cm/1000 year)(2.6 g/cm 3 )(1.5 E18 cm 3 ) = 9.36 E15 g/year. (9.36 E15 g/year)(10 E-6 g lead/g land) = 93.6 E9. 11. 180,000 tons/year from natural weathering of rocks (Volesky, 1990). 20. Land to atmosphere: 5.9 E9 g/year (Lantzy and Mackenzie, 1979). L1401-frame-A4 Page 174 Monday, April 10, 2000 10:25 AM © 2000 by CRC Press LLC BIOGEOCHEMICAL CYCLE OF LEAD AND THE ENERGY HIERARCHY 175 Table A4.3 Emergy per Mass and Concentration of Lead Graphed in Figure 4.7 Note Item Concentration (g/m3) Emergy per Mass (sej/g) 1 Ocean 3 E-5 0 2 Inland cycle 16 1 E9 3 Recycled in wetland 100 1.7 E9 4 Lead core 6.55 E4 4.5 E9 5Refined lead 11.3 E6 7.3 E10 Notes: g = gram; m 3 = cubic meter; sej = solar emjoules; cm 3 = cubic centimeter. 1. Zero emergy when no further dispersion is possible (no available energy in the concentration); ocean has lowest lead concentration of the main phases of the geobiosphere (Garrels, Mackenzie, and Hunt, 1975). 2. Assigned a share of the global emergy contribution to the continental earth cycle (Kuroda, 1982; Drever et al., 1988). Transformity is that of the land cycle = (9.44 E24 sej/year)/(9.36 E15 g/year) = 1.0 E9 sej/g. 3. Evaluated from wetland system containing lead (Figure 4.7). Emergy in support, 6.3 E10 sej/m 2 /year from Table 5.4 divided by 0.1 g/m 2 /day from Figure 8.2 times 365 days/year = 1.73 E9 sej/g. See Figure 4.6. Concentration in wetland = 100 ppm. 4. Assigned a share of the global emergy contribution (9.44 E24 sej/year) to the earth cycle in maintaining orographic uplift (2.15 E15 g/year). Lead in ore, 6.55% (Kesler, 1978). 5. Emergy per gram from Pritchard, Appendix A11, Figure A11.7 and Table A11.6; lead per volume = (11.3 g/cm 3 )(1 E6 cm 3 /m 3 ) = 11.3 E6 g/m 3 . L1401-frame-A4 Page 175 Monday, April 10, 2000 10:25 AM © 2000 by CRC Press LLC 177 A PPENDIX A5 A Field Measurement Methods Lowell Pritchard, Jr. This appendix provides details for the diurnal oxygen method for primary production under water, for using leaf area index for production by emergent plants, for tests of toxicity by planting seedlings, and for the study of small invertebrate animals and their biodiversity. DIURNAL OXYGEN MEASUREMENTS Gross primary productivity and community respiration were estimated for underwater components (submerged and algae) with diurnal oxygen measurements every 3 h over a 24-h period. Dissolved oxygen measurements were made with an oxygen meter (YSI model 54A) with the probe attached to a 2-m rod. the probe was gently moved about in the water at a depth of about 20 cm to provide current necessary for electrode operation. Temperature was recorded at the time of measurements. Several standard Winkler titrations were performed to confirm D.O. meter readings, using the azide modification (American Public Health Association, 1985). Sampling was done with a BOD bottle (300 ml) in a sampler designed to minimize aeration during collection. The sampler was extended on a 3-m pole held forward so that gas bubbles released from the sediments by footsteps would not influence the composition of the sample. Reagents were added, and titrations were carried out within a few hours. CALCULATION OF DIFFUSION CONSTANT Based on movement of dye and water depth, a diffusion coefficient was calculated each time according to the Bansal equation (Bansal, 1973). The very slow rates of water movement in open water areas of Steele City Bay were estimated using a drop of dye, stopwatch, and a meter stick. Rates of dye front movement were calculated. Surface water turnover as shown by dye movement was related to wind movement and proximity to windbreaks, and the fact that the winter measure- ments gave a higher diffusion coefficient was due to greater windiness. The summer 1990 conditions were similar for all sites, but the winter 1991 wind and water movement conditions were variable, so the sites were broken into three groups and a different average value for water velocity was applied to each group. Rates of flow and water depth are the two parameters that determine the overall reaeration coefficient in the empirical work of Churchill et al. (1962) and the analysis of Bansal (1973). Bansal gives the reaeration coefficient relationship as the general formula L1401-frame-A5 Page 177 Monday, April 10, 2000 10:32 AM © 2000 by CRC Press LLC 178 HEAVY METALS IN THE ENVIRONMENT: USING WETLANDS FOR THEIR REMOVAL where K 2 = reaeration coefficient in reciprocal seconds. To convert K 2(base e) , K 2(base 10) was multiplied by 2302. The effect of temperature on the reaeration coefficient is given by the following empirical relationship (Bansal, 1973): When this form of the reaeration coefficient is used, results are given as concentration change per unit time (dC/dt) rather than mass flux per area per unit time (dm/dt), because the depth of water is included in the calculation of the reaeration coefficient. A separate calculation is required for every depth and velocity condition. The formula for change in gas concentration due to diffusion comes from the two-film theory of gas transfer (Metcalf and Eddy Inc., 1979) and can be expressed as where dC/dt = change in concentration, ppm h –1 K 2 = diffusion coefficient h –1 C s = saturation concentration of oxygen in solution, ppm C = concentration of oxygen in solution, ppm The diffusion coefficient is sometimes expressed as total oxygen flux across the water surface per hour (g O 2 m –2 h –1 ) for a 100% oxygen deficit (i.e., 0% saturation). At a 100% oxygen deficit, C above = 0, and the change in the concentration equation reduces to Units of ppm-h –1 are equivalent to g m –3 h –1 , so multiplying by depth in meters yields the desired units of g O 2 m –2 h –1 at 100% oxygen deficit. These values are given in Table A5 A .1. They are comparable to values for the diffusion coefficient given by Odum (1956), which range from 0.03 to 0.08 g O 2 m –2 h –1 for still water. The diurnal curve method of calculating metabolism was used (Odum, 1985). From the raw data for dissolved oxygen concentration and temperature, rates of change were calculated. Oxygen deficit or excess was determined from a table of solubilities (American Public Health Association, 1985). From the diffusion-corrected rate-of-change curve for oxygen, gross production, net production, and community respiration were determined graphically using a compensating polar planimeter (see Figure 5.4). As a simplification, respiration was calculated to increase linearly throughout the day. WATER LILY LEAF AREA INDEX The leaf area index of floating vegetation was measured using a line-intercept transect 5 m in length. The intercept lengths were recorded for individual leaves of Nymphaea . Totals of intercept lengths divided by transect length gave a value for the leaf area index. K 2 base 10, 20°C() cV a D b = K 2T°() K 220°() ∗ 1.016() T20– = dC dt K 2 base e() ∗ C s C–()= dC dt K 2 C s = L1401-frame-A5 Page 178 Monday, April 10, 2000 10:32 AM © 2000 by CRC Press LLC FIELD MEASUREMENT METHODS 179 CANOPY LEAF AREA INDEX Leaf area index for ( Nyssa ) trees in areas of very low canopy coverage (locations F and G) was estimated by grouping branches into size classes, visually estimating (from the ground) leaves per branch for each class, and branches per trunk, for five trunks of known diameter in each sample area. The length and width of 100 leaves from each sample area were measured. The area of each leaf was calculated assuming elliptic proportions (area = π ab, where a and b are the lengths of the semiaxes). Average leaf area was multiplied by leaves per trunk to obtain total leaf area for five trunks. The total leaf area per unit basal trunk area was calculated and multiplied by the total basal area of trees in marked plots (see below under Woody plant sampling). This number, divided by the area of the plots, gave a leaf area index. The leaf area index for areas of much higher canopy coverage was estimated using a vertical line-intercept method. Using a bow and arrow, a string was shot vertically into the canopy. Leaves touching the string were counted. This procedure was repeated at 20 different points. If the area overhead was open sky, a value of zero was recorded. Leaf area index was also calculated from collected litterfall. Litterfall baskets were attached to trees in all plots in forested areas (F, G, H, and the reference forest; see Figures 1.3 and 5.2). Litter was collected on each field trip, separated into leaves and other material, dried, and weighed. An area/mass ratio was determined for dried leaves by weighing uniformly punched circles of known area. Petiolar mass was subtracted from the collective leaf mass, and the area/mass ratio was used to convert the corrected leaf mass to leaf area. The leaf areas were summed over the year Table A5 A .1 Calculation of Reaeration Coefficient from Measured Water Velocity and Depth According to Bansal Equation Site Velocity (ft s –1 ) ±S.E. Depth (ft) K 2(base 10,20°C) (s –1 ) K 2(base e,20°C) (h –1 ) Oxygen flux at 100% deficit (g O 2 m –2 h –1 ) Winter B 0.017 0.007 2.62 0.000001 0.010 0.064 C 0.017 0.007 2.46 0.000001 0.011 0.066 D 0.017 0.007 2.95 0.000001 0.009 0.061 F 0.017 0.007 1.15 0.000003 0.032 0.089 G 0.017 0.007 1.64 0.000002 0.019 0.077 Summer A 0.106 0.031 1.80 0.000006 0.051 0.299 B 0.037 0.005 2.95 0.000001 0.014 0.131 C 0.037 0.005 2.79 0.000001 0.015 0.134 D 0.016 0.001 3.28 0.000000 0.007 0.075 F 0.016 0.001 2.13 0.000001 0.013 0.089 G 0.037 0.005 2.30 0.000002 0.019 0.145 RP 0.106 0.031 2.30 0.000004 0.036 0.271 Note: D = depth of water column. V = water velocity. c = 0.000054 s –1 at 20°C. a = 0.6 a constant. b = –1.4, a constant. s = seconds; ft = feet; h = hours; g = grams. K 2 = aeration coefficient using logarithm to the base 10. From Bansal, 1973. K 2(base1 0,20°C) = cV a /D b , where a = 0.6, b = 1.4, and c = 0.000054. L1401-frame-A5 Page 179 Monday, April 10, 2000 10:32 AM © 2000 by CRC Press LLC 180 HEAVY METALS IN THE ENVIRONMENT: USING WETLANDS FOR THEIR REMOVAL and divided by the area of the trip to determine the leaf area index for the leaf fall shadow of the tree (assuming on average a vertical drop). For locations without closed canopies, the calculated leaf area index was multiplied by the fraction of the area actually canopied to calculate the overall leaf area index for the location. For the 20 × 20-m plots in locations F and G, the canopied fraction of the plot was estimated by counting Nyssa greater than 10 cm dbh and multiplying by their estimated individual canopy area. PRODUCTION SUMMARY The leaf area index for the reference forest canopy (control pond, station RF) was converted to a gross primary productivity value using an LAI/gross primary productivity linear regression from data on wetland forests given by Brown et al. (1984). Gross primary productivities for the other areas were assigned in proportion to their relative leaf area indices. Gross primary production was calculated for Nymphaea by setting the highest leaf area index equal to two times a conservative estimate of freshwater marsh net primary production (= 1000 g dry weight/m 2 ; Mitsch and Gosselink, 1986). Productivities for other locations were assigned based on the ratios of leaf area indices. For both trees and water lilies the energy conversion value of 4.5 kcal/g dry weight was used (E.P. Odum, 1983). Aquatic gross primary production reported above in terms of g O 2 m –2 day –1 was converted to energy terms using the conversion of 3.5 kcal/g O 2 from the simple formula for photosynthesis (Cole, 1975). MACROINVERTEBRATES At each sample location, five cores 7.7 cm in diameter and 10 cm in depth were taken with a cylindrical mini-Wilding-type sampler designed to isolate a portion of the water column above the sediment. The sampled material was transferred to a U.S. Standard No. 30 sieve bucket (Weber, 1973). Fine particulates were removed in the field by partially submerging and agitating the bucket, taking care not to allow exchange of materials except through the sieve bottom. Remaining material was drained, placed in screw-top 1-gal plastic containers, labeled, and then saturated with rose bengal stain solution. After a few hours the stain solution was drained. Since the peaty material retained a significant amount of water, 90% ethanol was added as a preservative, rather than the recommended 70%. PROCESSING, IDENTIFICATION, AND ANALYSIS From each sample, small aliquots were removed, washed under water in a No. 30 sieve, and placed in a water-filled pan (Weber, 1973). Macroinvertebrates visible to the naked eye were removed with forceps and stored in vials in 70% ethanol. This was repeated for the entire sample. Whole specimens were identified to the family level, with the exceptions of crustaceans, gastropods, and oligochaetes. Where specimens were damaged, only portions with heads were counted in the analysis. Early instars and pupae were identified to the lowest reliable level. Chironomidae were separated into feeding guilds, and Culicidae were identified to genus or to species where possible. References for identification included Pennak (1978), McCafferty (1981), and Merritt and Cummins (1984). Data collected were summarized for taxonomic groups. Densities (individuals/area), family richness (number of families/sample), and diversity indices were calcu- lated for each sample (Tables A5 B .2 and A5 B .3). L1401-frame-A5 Page 180 Monday, April 10, 2000 10:32 AM © 2000 by CRC Press LLC FIELD MEASUREMENT METHODS 181 DIVERSITY INDICES Diversity was calculated using three indices. The Shannon diversity index is given by where H ′ is the information in bits per individual, p i is the proportion of individuals in a sample belonging to taxon i, and n is the total number of taxa in the sample. Sample variance of H ′ is given by (Zar, 1984), where N is the total number of individuals in the sample, f i is the frequency of observation of each taxon, and the degrees of freedom are Simpson diversity was calculated using the dominance measure Simpson diversity is then simply with variance Margalef’s (1968) diversity index was calculated as where S is the total number of taxa in the sample. SEEDLING SURVIVAL To determine whether regeneration by seedling had been hindered either by the toxicity of metals in the sediments or by flooding, seedlings of bald cypress ( Taxodium distichum ), pond cypress ( T. ascendens ), and blackgum ( Nyssa sylvatica var. biflora ) were planted on recently H′ p i p i () 2 ln i1= n ∑ = s 2 Σf i f 2i ln() 2 Σf i f 2i ln() 2 N⁄– N 2 = DF s 1 2 s 2 2 +() 2 s 1 2 () 2 N 1 s 2 2 () 2 N 2 + = L Σn 1 n 1 1–() NN 1–() = D s 1L–= s 2 4 Σp i 3 Σp i 2 () 2 –[]N⁄= Ma S1–() N 2 ln = L1401-frame-A5 Page 181 Monday, April 10, 2000 10:32 AM © 2000 by CRC Press LLC [...]... AII-BG 151 .3 AIII-AG 10.6 AIII-BG 959.0 AIV-AG 164.6 AIV-BG 762.9 AV-AG 87.6 AV-BG 444.1 AVI-AG 267.5 AVI-BG 585.0 AVII-AG . 180 HEAVY METALS IN THE ENVIRONMENT: USING WETLANDS FOR THEIR REMOVAL and divided by the area of the trip to determine the leaf area index for the leaf fall shadow of the tree (assuming on. analysis was performed. L1401-frame-A6 Page 187 Tuesday, April 11, 2000 3:02 PM © 2000 by CRC Press LLC 188 HEAVY METALS IN THE ENVIRONMENT: USING WETLANDS FOR THEIR REMOVAL DETERMINING SEQUENTIAL. L1401-frame-A5 Page 183 Monday, April 10, 2000 10:32 AM © 2000 by CRC Press LLC 184 HEAVY METALS IN THE ENVIRONMENT: USING WETLANDS FOR THEIR REMOVAL Table A5B.2 Benthic Macroinvertebrate Sampling Location Taxon