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1768 Notes<br />

coming tide over a broad tidal sand flat. Estuarine<br />

Coastal Shelf Sci. 32: 4054 13.<br />

PHINNEY, D. A., AND C. S. YENTSCH. 1985. A novel<br />

phytoplankton chlorophyll technique: Toward automated<br />

analysis. J. Plankton Res. 7: 633-642.<br />

RIISGARD, H. U., AND F. MBHLENBERG. 1979. An improved<br />

automatic recording apparatus for determining<br />

the filtration rate of MytiZus edulis as a function<br />

of size and algal concentration. Mar. Biol. 52: 6 l-67.<br />

SMITS, A. J., AND D. H. WOOD. 1985. The response of<br />

turbulent boundary layers to sudden perturbations.<br />

Annu. Rev. Fluid Mech. 17: 321-358.<br />

STOECKER, D. K., A. E. MICHAELS, AND L. H. DAVIS. 1987.<br />

Large proportion of marine planktonic ciliates found<br />

to contain functional chloroplasts. Nature 326: 79&<br />

792.<br />

SVANE, I., AND M. OMPI. 1993. Patch dynamics in beds<br />

of the blue mussel MytiZus edulis L.: Effects of site,<br />

patch size and position within a patch. Ophelia 37:<br />

187-202.<br />

THOMPSON, R. J., AND B. L. BAYNE. 1972. Active metabolism<br />

associated with feeding in the mussel A4ytiZu.s<br />

edulis L. J. Exp. Mar. Biol. Ecol. 9: 111-124.<br />

TROWBRIDGE, J. H., W. R. GEYER, C. A. BuT)~~AN, AND R.<br />

J. -MAN. 1989. The 17-Meter Flume at the<br />

Coastal Research Laboratory. Part 2: Flow charac-<br />

teristics. Woods Hole Oceanogr. Inst. Tech. Rep.<br />

WHOI-89-1 1, CRC-89-3. 37 p.<br />

WILDISH, D. J., AND D. D. KRISTMANSON. 1979. Tidal<br />

energy and sublittoral macrobenthic animals in estuaries.<br />

J. Fish. Res. Bd. Can. 36: 1197-1206.<br />

- 1984. Importance to mussels of the<br />

bend boundary layer. Can. J. Fish. Aquat. Sci. 41:<br />

1618-1625.<br />

- AND OTHERS. 1987. Giant scallop feeding and<br />

growth responses to flow. J. Exp. Mar. Biol. Ecol. 113:<br />

207-220.<br />

-, D. D. KRISTMANSON, AND A. M. SAULNIER. 1992.<br />

Interactive effect of velocity and seston concentration<br />

on giant scallop feeding inhibition. J. Exp. Mar. Biol.<br />

Ecol. 155: 161-168.<br />

-, AND M. P. MIYARES. 1990. Filtration rate of blue<br />

mussels as a function of flow velocity: Preliminary<br />

experiments. J. Exp. Mar. Biol. Ecol. 142: 213-219.<br />

-, AND A. M. SAULNIER. 1992. The effect ofvelocity<br />

and flow direction on the growth ofjuvenile and adult<br />

giant scallops. J. Exp. Mar. Biol. Ecol. 155: 133-143.<br />

Submitted: 24 December 1992<br />

Accepted: 5 April 1994<br />

Amended: 8 June 1994<br />

Limnol. Oceanogr., 39(7), 1994, 1768-1779<br />

Q 1994, by the American society of Limnology and -w-why, Inc.<br />

Plaster standards to measure water motion<br />

Abstract-Plaster of paris blocks (clod cards) were<br />

re-evaluated as devices to measure water motion in<br />

freshwater and marine environments. Clod cards,<br />

developed in 1971, have only been used as indicators<br />

of relative water motion. We generated standard<br />

curves relating the dissolution rates of clod cards to<br />

water speed, temperature, and salinity by attaching<br />

the cards to a mechanical arm rotating in a tank of<br />

water. Free convection experiments were also conducted<br />

by suspending clod cards in quiescent solutions<br />

held in ice chests. We describe calibration<br />

methods that use either forced convection or free<br />

convection to correct field results for the effects of<br />

temperature and salinity on dissolution rates of clod<br />

cards. Although dissolution rates were lower in freshwater<br />

than brackish or seawater, salinity in the range<br />

of 20-4wm did not greatly affect dissolution. Properly<br />

calibrated, clod cards now offer a simple, practical<br />

method for measuring integrated water motion, expressed<br />

in readily visualized rate units, over a wide<br />

range of temperatures, salinities, and water speeds.<br />

Water motion is of fundamental importance<br />

to the growth of lower aquatic organisms, affecting<br />

those metabolic processes such as photosynthesis<br />

and respiration which depend on<br />

chemical exchange with the environment across<br />

transfer surfaces (Patterson 1992). Corals (e.g.<br />

Jokiel and Morrissey 1986, 1993), phytoplankton<br />

(e.g. Laws 1975), and seaweeds (e.g.<br />

Mathieson et al. 1977; Glenn and Doty 1992)<br />

are examples of organisms whose distribution<br />

and growth rates are determined by rates of<br />

water motion in the environment. Despite its<br />

importance, there is no commonly accepted<br />

field method for measuring integrated water<br />

motion over the time scales (hours or days)<br />

relevant to the growth rates of aquatic organisms.<br />

Doty (197 1) and Muus (1968) independently<br />

proposed using dissolution rates of calcium<br />

sulfate (plaster of paris) blocks or spheres<br />

to estimate water motion. However, they and<br />

subsequent users (e.g. Mathieson et al. 1977)<br />

reported problems of undetermined effects of


Notes 1769<br />

salinity and temperature on results. Nevertheless,<br />

the clod cards proposed by Doty are easily<br />

prepared with standard ice-cube trays as molds<br />

and are suited to marine studies because they<br />

are large enough to be left out through a tide<br />

cycle without dissolving completely. It is a<br />

convenient and inexpensive method of measuring<br />

water motion in field studies. We have<br />

attempted to define the behavior of clod cards<br />

with respect to temperature and salinity and<br />

to develop calibration methods to enhance their<br />

usefulness.<br />

In his original description, Doty (197 1) recommended<br />

expressing field results as a “diffusion<br />

increase factor” (DF), defined as the<br />

ratio of weight loss of clod cards placed in the<br />

field to the weight loss of clod cards from the<br />

same batch held under specified still-water<br />

conditions in the laboratory. DF was meant to<br />

express the multiplication factor of diffusion<br />

in the field relative to diffusion in the absence<br />

of water motion. Unfortunately, his reported<br />

still-water values sometimes varied inexplicably<br />

among batches of clod cards that had<br />

been prepared and measured the same way.<br />

This variation introduced a large potential error<br />

into the calculation of DF, since this relatively<br />

small number is used as a divisor.<br />

Doty’s laboratory calibration method consisted<br />

of placing five clod cards on the bottom<br />

of a 15-cm-diameter container to which 2 liters<br />

of test solution were added. The water (motionless)<br />

was changed every day for 4 d. The<br />

initial and final dry weights of the clod cards<br />

were used in the DF calculations. Howerton<br />

and Boyd (1992) as well as Jokiel and Morrissey<br />

(1993) have demonstrated that the calibration<br />

container must have a minimum volume<br />

of 20 liters per clod card if it is to accurately<br />

represent weight loss due to diffusion in totally<br />

calm water.<br />

An additional problem is created by stratification<br />

in the calibration container, particu-<br />

larly when the clod cards are placed on the<br />

bottom. When a solid dissolves in quiescent<br />

water, material from the solid dissolves and<br />

diffuses away from the surface, producing a<br />

solution near the solid that is denser than the<br />

water itself. This solution flows downward, and<br />

the resulting flow increases the dissolution rate.<br />

However, the dense solution may “pool” on<br />

the bottom of the container, creating a layer<br />

of solution with a higher concentration of the<br />

dissolving material than in the bulk liquid. If<br />

the dissolving solid is placed on the bottom of<br />

the container, it will generate a layer of relatively<br />

concentrated liquid that will retard the<br />

dissolution rate compared to the solid in pure<br />

bulk solution.<br />

In unpublished experiments pointing the way<br />

to an improvement in methodology, Doty attached<br />

clod cards to a rotating arm in a tank<br />

of seawater and found that the dissolution rates<br />

of the cards were proportional to the rate at<br />

which they moved through the water. He called<br />

the apparatus a “water motion simulator”<br />

(WAMOSI) because it was the clod card, not<br />

the water, that was moving. The raw data tabulation<br />

of that study (Doty et al. 1986) shows<br />

that despite differences in apparent still-water<br />

dissolution rates among different batches of<br />

clod cards, their actual dissolution rates on the<br />

rotating arm were reproducible at a given velocity.<br />

Subsequently, Glenn and Doty (1992)<br />

used the rotating-arm calibration method in<br />

combination with field measurements to show<br />

that 85-98% of the variability of growth rates<br />

of eucheumatoid red seaweeds across seasons<br />

on a reef flat in Hawaii could be explained by<br />

water motion. These experiments indicated<br />

that calibrated clod cards would be valuable<br />

tools for correlating growth rates with water<br />

motion in the marine environment.<br />

Recently, Howerton and Boyd (1992) used<br />

clod cards to measure circulation patterns in<br />

aquaculture ponds, and Jokiel and Morrissey<br />

(1993) used clod cards to study water motion<br />

on coral reefs. In both studies, the investigators<br />

improved the still-water calibration method<br />

by increasing the volume of water into which<br />

the cards dissolve, and they measured rates of<br />

still-water dissolution of the cards as functions<br />

of duration of exposure, temperature, and salinity.<br />

Both studies used a rotating arm to estimate<br />

dissolution rates as a function of water<br />

velocity at a single temperature and salinity.<br />

They concluded that clod cards were valuable<br />

in measuring relative rates of water motion<br />

but, similar to earlier investigators, cited the<br />

need for equations relating card dissolution<br />

rates to fluid velocity as influenced by temperature<br />

and salinity before they could be used<br />

to measure absolute water velocities. Deriving<br />

and validating these equations was the purpose<br />

of our study.<br />

Clod cards were prepared essentially ac-


1770 Notes<br />

r=0.15<br />

(typ.)<br />

‘F q-<br />

El<br />

_<br />

I<br />

/‘ ‘\,<br />

+45cm+<br />

/F$2+.,<br />

\<br />

3.3cm<br />

T=T<br />

Bottom surface sanded<br />

to adjust weight<br />

to 30 f 1.5 g<br />

Fig. 1. Dimensions of the clod cards.<br />

cording to the methods of Doty (197 1) and<br />

Howerton and Boyd (1992), except that neither<br />

the starting plaster of paris nor the finished<br />

cards were oven-dried before use. Our clod<br />

cards were made from reagent-grade plaster of<br />

paris (calcium sulfate hemihydrate, EM Science<br />

Co.) with 335 ml of water per 500 g. We<br />

slowly added plaster of paris to the water<br />

as we stirred it with a spoon; we poured the<br />

slurry into flexible plastic ice-cube trays and<br />

allowed it to harden for 20-30 min before removing<br />

the clod cards. We tapped the trays<br />

vigorously several times while the mixture was<br />

still liquid to dislodge air bubbles. Sometimes,<br />

a thin layer of liquid covered the surface of the<br />

hardening clod cards in the trays. This layer<br />

was decanted before the cards were removed.<br />

After removal, the cards were dried for 3 d or<br />

longer on a laboratory bench, and the bottoms<br />

were sanded until the cards had uniform weight<br />

within a batch (within 1.5 g); they were then<br />

glued to 5- x 7-cm sheets of waterproof plastic<br />

(Nalgene PolyPaper) with silicone cement.<br />

Weight loss due to water exposure was quantified<br />

by weighing dry clod cards before exposure,<br />

placing them in the test solution for<br />

24 h, allowing them to redry for 3 d or longer<br />

on a laboratory bench, and then reweighing<br />

them.<br />

The ice-cube trays used in these experiments<br />

produced clod cards of shape and dimensions<br />

shown in Fig. 1. Internally, the dry cards had<br />

a foam structure with numerous interconnected<br />

minute air spaces within the calcium sulfate<br />

matrix. The cards had densities of 1.19-l .21<br />

/<br />

at 25°C and weighed 28-32 g each. When placed<br />

in test solutions, the cards were fully saturated<br />

within 5 min, absorbing from 10 to 12 ml of<br />

solution.<br />

Water motion experiments were carried out<br />

inside a greenhouse in a shallow, wooden-sided,<br />

square tank (2.1 m long, 0.36 m deep) with<br />

a plastic liner (Fig. 2). The tank was filled with<br />

test solution to a depth of 25 cm (solution<br />

volume, 1.1 m3) and covered with sheets of<br />

Styrofoam to control temperature during each<br />

24-h run. Test solutions were chilled by circulating<br />

the water through a 124-W refrigeration<br />

unit with external thermostat by means<br />

of a 30-W circulation pump. Solutions were<br />

heated with a thermostat-controlled, 150-W<br />

immersion heater.<br />

Clod cards were attached at various positions<br />

along a 2-m stainless steel arm (1 cm<br />

thick) which was rotated in the tank at 2.4 rpm<br />

by a 37-W electric gear motor secured over the<br />

middle of the tank by an external wooden<br />

framework. The cards were mounted on the<br />

arm by attaching them with rubber bands to<br />

rigid PVC-plastic plates (5 x 7.5 cm, 0.3 cm<br />

thick) screwed to the arm. Five cards were<br />

mounted along each of the two radii at distances<br />

from the center of 7, 27,47,67, and 87<br />

cm. Thus, each position was represented by<br />

duplicate cards moving through the water at<br />

nominal velocities ranging from 1.8 to 2 1.8<br />

cm s-l, which are within the range of water<br />

velocities encountered on tropical reef flats<br />

(Glenn and Doty 1992) but lower than extreme<br />

tidal bores, which are up to 80 cm s-l (Mathieson<br />

et al. 1977). Greater velocities can be<br />

achieved by selecting a gear motor with a higher<br />

rotation rate (Howerton and Boyd 1992) or<br />

by using a longer rotating arm (Jokiel and Morrissey<br />

1993).<br />

Dissolution rates under free convection conditions<br />

were determined by suspending clod<br />

cards by wires 5 cm below the surface of 60<br />

liters of solution contained in ice chests. The<br />

ice chests were kept under constant temperature<br />

in an undisturbed indoor location during<br />

each 4-6-d run. The cards were withdrawn and<br />

weighed wet each day, then replaced in the<br />

chests.<br />

Three solutions were tested in the water motion<br />

tank: tapwater, brackish water, and seawater.<br />

Tapwater was from the Tucson municipal<br />

supply, and seawater was collected from


Notes 1771<br />

T<br />

2.1 m<br />

mounted<br />

arm<br />

mounte~~~~a level<br />

k- 2.1 m 4<br />

Fig. 2. Design of the water motion simulator.<br />

a seaside well in the upper Gulf of California<br />

at Puerto Pefiasco, Sonora, Mexico. Brackish<br />

water was a 1 : 1 mixture of tapwater and seawater.<br />

Salinities by refractometer were 0, 20,<br />

and 407~. Solutions were measured for temperature,<br />

pH, and electrical conductivity at the<br />

start and finish of each run. Samples of each<br />

solution were analyzed for cations and anions,<br />

including calcium and sulfate, by AOAC<br />

methods (Laboratory Consultants, Tempe, Ar-<br />

Table 1. Analyses of tapwater, brackish water, and seawater<br />

used in clod card calibration experiments.<br />

Constituent<br />

Tapwater 20%3 40%<br />

Calcium 1.46 7.06 13.20<br />

Sulfate 0.85 16.66 33.94<br />

Boron 0.008 * 0.473<br />

Magnesium 0.417 * 61.6<br />

Sodium 2.13 * 534.8<br />

Chloride 1.71 * 630.4<br />

Fluoride 0.056 * 0.078<br />

PH 8.1-8.5 8.1-8.2 8.2-8.3<br />

EC (mmhos cm-‘) 715 34,000 71,500<br />

* Brackish water (20%~) was a I : 1 mixture of tapwater and 40% water. Analyses<br />

of elements of limited importance to this study were omitted for this<br />

mixture.<br />

(mol<br />

m-l)<br />

izona, and the Soil and Water Testing Laboratory,<br />

University of Arizona, Tucson) (Table<br />

1). Solutions in the tank were changed after 2-<br />

3 runs of clod cards to reduce accumulation<br />

of calcium sulfate in the water. The ice-chest<br />

experiments used an additional solution, 25o/oo<br />

salinity, also prepared by dilution of tapwater<br />

and seawater.<br />

Weight loss of clod cards vs. water motion<br />

is expected to be a decreasing rather than a<br />

linear function, because the exposed area of<br />

the clod diminishes as dissolution proceeds.<br />

The rate of dissolution of a solid in an aqueous<br />

solution can be expressed as<br />

dW<br />

- = -kAAC.<br />

d6<br />

W is the weight of the solid, 8 is time, k the<br />

mass transfer coefficient, A the exposed area<br />

of the solid, and AC the concentration difference<br />

between the dissolved solid in the liquid<br />

at the solid-fluid interface and in the bulk liquid.<br />

The dissolution of solids, including the diffusion<br />

process across boundary layers, is described<br />

in detail in several mass transfer texts


1772<br />

Notes<br />

J<br />

1.0<br />

2<br />

E 0.9<br />

L<br />

2 0.6<br />

P<br />

< 0.7<br />

t 0.6<br />

0.010<br />

1 10 100<br />

Velocity, cm s-1<br />

Fig. 3. Plot ofclod card weight loss vs. velocity through<br />

32o/oo seawater for data from Glenn and Doty (1992) used<br />

in the form of Eq. 3 (their data extend to higher velocities<br />

than our work). The slope of the regression line is<br />

0.838kO.042.<br />

0.5<br />

0.4 r I<br />

0 5 10 15 20 25 30<br />

Temperature, "C<br />

Fig. 4. Correction factor for clod card data with T,, =<br />

298°K and pref = viscosity of pure water at 25°C. The four<br />

lines correspond to salinities of 0, 10, 20, and 40%~ from<br />

top to bottom. Calculated with viscosity data from Riley<br />

and Skit-row (1975).<br />

(e.g., Cussler 1984; Sherwood et al. 1975; Skelland<br />

1974). For solids of sample geometries<br />

which dissolve uniformly, the area and weight<br />

relationship can be approximated as<br />

A (2)<br />

Ai and Wi represent the initial area (exposed)<br />

and weight of the solid. For clod cards, this<br />

approximation is useful until > 50% of the clod<br />

has dissolved or longer, depending on the velocity<br />

of the fluid.<br />

The mass transfer coefficient is also influenced<br />

by the change in clod dimensions; however,<br />

the effect is usually minor until well into<br />

the dissolution process. Equations 1 and 2 can<br />

be combined and integrated to give<br />

1 - (?r = ;k($A,. (3)<br />

Wr is the final weight of the clod after time 8<br />

has elapsed. Equations 3 is useful for data analysis;<br />

the mass transfer coefficient usually varies<br />

with the fluid velocity raised to a power (P),<br />

so a log-log plot of [l - (WJ/ Wi)“] against<br />

velocity should yield a straight line. This is<br />

illustrated in Fig. 3 with the data of Glenn and<br />

Doty (1992). Equation 3 can be rearranged to<br />

give an expression for the overall fraction of<br />

weight 10~s (A W/ Wi):<br />

Assuming that AC remained constant during<br />

dissolution, experimental data at a given temperature<br />

and salinity were correlated with the<br />

model<br />

( )<br />

l/3<br />

Wf = aVm.<br />

I- j7<br />

I<br />

The constants a and m can be determined experimentally<br />

by means of the rotating arm, and<br />

weight loss data from clod cards exposed in<br />

the field can then be used in Eq. 5 to determine<br />

water motion.<br />

The effect of temperature at a given salinity<br />

and CaSO, concentration was corrected by using<br />

the group (T/T,,) (p,.,&) to normalize data<br />

to a reference temperature, where Tis absolute<br />

temperature, and p is viscosity. This group (Fig.<br />

4) is typically used to estimate the changes in<br />

diffusion coefficients (Reid and Sherwood<br />

1966) with varying solution strength.<br />

From Eq. 1 and 3, the dissolution rates are<br />

also dependent on the concentration of CaSO,<br />

in the bulk water and factors influencing the<br />

concentration, such as the ionic strength of the<br />

bulk water. To determine the concentration<br />

difference, we assume the solution at the gypsum-water<br />

interface is saturated with CaSO,<br />

and determine AC with the solubility product<br />

as<br />

Ksp = [Ca2+]i[S042-]i<br />

g= 1 - 11 - ;k($)ACO13. (4)<br />

or<br />

= ([Ca’+], + AC)([S042-]b + AC) (6)


Notes<br />

1773<br />

0.022<br />

30<br />

0.020<br />

i b 0.019<br />

c -<br />

5 0.016<br />

E<br />

- 0.017<br />

2<br />

0.016<br />

I<br />

0.015<br />

25<br />

I<br />

2 20<br />

0<br />

c g 15<br />

8<br />

2<br />

10<br />

5<br />

Corrected Velocity _<br />

0.014<br />

u 5 10 15 20 25 30 35 40<br />

Salinity, 20<br />

0 A<br />

0<br />

30 40 50 60<br />

Rodius. cm<br />

Fig. 5. Calculated concentration difference of CaSO,<br />

between the solid-liquid interface and bulk solution of<br />

clod cards in natural seawater sources based on Eq. 7.<br />

Curve A was calculated based on literature values of seawater<br />

chemical content at 32%1 and assuming that seawater<br />

was diluted with distilled water to achieve the lower salinities;<br />

curve B was calculated based on chemical analyses<br />

of Puerto Peiiasco seawater at 40?&0 and Tucson tapwater<br />

used as the diluent in our study.<br />

Ac =<br />

1(<br />

_<br />

[Ca2+lb + W42% 2 + K Oo5<br />

2 1<br />

SP<br />

I<br />

Ka2+lb + W42- lb<br />

2 ) . (7)<br />

[Ca2+]i, [Ca2+lb, [S042-]i, and [S042-]b are calcium<br />

and sulfate ion concentrations at the interface<br />

and in the bulk solution. Ksp is the solubility<br />

product, which can be computed by the<br />

expressions given by Marshall and Slusher<br />

(1968), who allow for the presence of ion pairs<br />

such as MgS040 in their correlations.<br />

The values of [Ca2+16 and [S042-]b used in<br />

Eq. 7 are based on the total calcium and sulfate<br />

measured in solution; we have made no attempt<br />

to correct these concentrations for the<br />

presence of ion pairs containing calcium or<br />

sulfate. Increasing the ionic strength (or salinity)<br />

increases the CaSO, solubility product,<br />

thereby increasing the gradient between the interface<br />

and the bulk solution and accelerating<br />

the dissolution rate of a clod card. However,<br />

this effect is counteracted if the concentration<br />

of CaSO, in the bulk solution increases with<br />

salinity, which is the case with seawater; the<br />

seawater used in our experiments contained<br />

CaSO, at concentrations more than eight times<br />

that of the freshwater supply. The brackish<br />

supply, prepared by dilution, was intermediate.<br />

Figure 5 contains salinity correction curves<br />

Fig. 6. Correction for the induced-water-motion effect<br />

of the rotating arm in the tank. Top line is the velocity of<br />

the clod card in the tank at each position on the arm;<br />

bottom line is the velocity of the water in the tank estimated<br />

by the movement of suspended particles in the<br />

water; middle line is the corrected velocity used to correlate<br />

the card dissolution rates with water motion.<br />

based on Puerto Peiiasco seawater and Tucson<br />

tapwater used in our study (curve B) and on<br />

literature values of normal seawater constituents<br />

(Hansson 1973) assumed to be diluted<br />

with distilled water (curve A). Curve B falls<br />

below curve A because Tucson tapwater and<br />

Puerto Pefiasco seawater contain proportionally<br />

more CaSO, than distilled water and standard<br />

seawater.<br />

The water motion tank was used to obtain<br />

data for velocity-weight loss correlations. The<br />

velocity of the clod card through the water was<br />

easily calculated from the rotation rate of the<br />

arm and the distance of the card from the center<br />

of rotation. However, it was necessary to<br />

correct for the rotary movement imparted to<br />

the water in the tank by the moving arm. This<br />

movement was determined at each of the five<br />

positions by measuring the movement of small<br />

suspended particles in the water. A drag model<br />

was correlated to the data and used to correct<br />

the velocities of the cards into estimates of<br />

their velocities relative to the water at each<br />

position (Fig. 6). The correction was more significant<br />

at low than at high velocities.<br />

Forced convection tests were run at temperatures<br />

from 13 to 35°C in three different<br />

salinities on the rotating arm (Fig. 7). Plots in<br />

the form of Eq. 5 were subjected to regression<br />

analyses (Table 2). In all runs, clod card weight<br />

loss at the lowest test velocity was increased<br />

by free convection, and the points fell - 15%<br />

above the curve of best fit to the other points;


1774 Notes<br />

0.6<br />

A 25.5’<br />

A 30.5.<br />

0 33.5.<br />

Table 2. Regression analyses of clod card runs at various<br />

salinities and temperatures. The model equation was<br />

in the form [ 1 - (WI W,)]” = a I/‘“; both sides of the equation<br />

were converted to natural logarithms to reduce the<br />

equation to a linear function for analysis.<br />

a<br />

0 2 4 6 6<br />

Velocity. cm a-l<br />

14 16<br />

20<br />

0 13.0 8 0.0146 0.653 0.992 3.16<br />

0 19.5 8 0.0126 0.749 0.992 3.67<br />

0 25.5 8 0.0157 0.772 0.997 2.49<br />

0 30.5 8 0.0178 0.750 0.984 5.33<br />

0 33.5 8 0.0187 0.799 0.996 2.81<br />

20 12.0 8 0.0141 0.765 0.988 4.73<br />

20 19.0 8 0.0136 0.823 0.991 4.43<br />

20 25.5 8 0.0164 0.867 0.990 4.75<br />

20 30.7 8 0.0180 0.868 0.997 2.95<br />

40 13.0 8 0.0130 0.768 0.994 3.24<br />

40 24.5 8 0.0183 0.793 0.998 2.53<br />

40 28.3 8 0.0307 0.757 0.987 4.84<br />

Temperature compensated<br />

0 40 0.0162<br />

20 32 0.0176<br />

40 24 0.0204<br />

0.745 0.965 6.94<br />

0.83 1 0.976 6.41<br />

0.773 0.984 4.93<br />

0.6<br />

V.”<br />

0 2 4 6 6 10 12 14 16 16 20<br />

Velocity, cm *-l<br />

0 13% (4O.h.) C<br />

0 2 4 6 6 10 12 14 16 16 20<br />

Velocity, cm se1<br />

Fig. 7. Temperature curves for clod cards run at different<br />

velocities in tapwater (A), brackish water (B), and<br />

seawater (C). Lines were fit to data points using Eq. 5.<br />

hence, data for the lowest velocity were omitted<br />

from curve fitting. The model equation can<br />

be used to calculate V as long as the velocity<br />

is >2 cm s-l.<br />

Coefficients of determination (r2) were 0.98<br />

or higher, and percent error of estimates of y<br />

were in the range 2.5-6.0%. Although m varied<br />

somewhat, the mean value was -0.8, the value<br />

expected for mass transfer from a flat surface<br />

in a turbulent flow (Skelland 1974). As expected,<br />

increased temperatures accelerated the<br />

dissolution rates of clod cards at all test salin-<br />

ities. For the temperature-compensated sequence<br />

of Table 2, [ 1 - ( Wr/ Wi)“] was divided<br />

by (T/T,,,) (P,&). Note that temperature-corrected<br />

data fell onto a response surface of the<br />

shape predicted by calculations of AC (Fig. 8).<br />

The effects of both temperature and salinity<br />

variations are included in the experimental data<br />

correlation (Eq. 8). Dissolution rates were lower<br />

in tapwater than in brackish water or seawater<br />

at a given temperature, but over the range<br />

20-40?& salinity had a minor effect on dissolution<br />

rates. Hence, salinity does not appear<br />

to be a major factor controlling dissolution<br />

rates in marine systems.<br />

The dimensional equation fitting our data is<br />

%=I -[I -0.71(~)($-Jy)<br />

(8)<br />

with Y = 0.985. The concemration difference,<br />

AC,, (mol liter-‘), is computed at 25°C by<br />

means of Eq. 7 or Fig. 4; 8 is expressed in days<br />

and V in cm s-l. The average ratio of Ai : Wi<br />

for our clod cards was 1.38 cm2 g- l.<br />

The results of mass transfer experiments are<br />

commonly reported in terms of the appropriate<br />

dimensionless groups, although most readers<br />

will likely find equations such as Eq. 8 more


Notes 1775<br />

Note: Data adjusted to 25%<br />

Fig. 8. Temperature-corrected data for clod cards run at different velocities in tapwater (O?%O), brackish water (20%0),<br />

and seawater (40%0). The data points are superimposed on a response surface based on Eq. 4 with k proportional to<br />

W.s and with AC calculated from Eq. 7 for Puerto Peiiasco seawater. Note that experimental data points fall on the<br />

response surface except at lowest velocity where free convection affects dissolution rates of the cards.<br />

convenient for use with marine systems since<br />

all the information required can usually be obtained<br />

from Figs. 4 and 5. Our forced convection<br />

data can also be described by the expression<br />

NSh = 0 . 059NgtN SC N - (9)<br />

Ns,, is the Sherwood number (kLID,), NRe the<br />

Reynolds number (L VP/~), and Nsc the Schmidt<br />

number (p/pDJ In the dimensionless groups,<br />

k is the mass transfer coefficient evaluated with<br />

Eq. 3 (with AC evaluated at solution temperature<br />

and salinity), D, the volumetric molecular<br />

difhtsion coefficient, p the viscosity, p the<br />

liquid density, and L a geometry term determined<br />

by the shape and orientation of the object.<br />

The geometry term introduced by Pasternak<br />

and Gauvin (1960) was used, where L<br />

= (surface area of body) + (perimeter of projected<br />

area perpendicular to flow). The mounting<br />

card was included in the calculation of the<br />

geometry term. The average value of L in these<br />

studies was 5.4 cm.<br />

Fluid properties were evaluated based on the<br />

bulk solution, with density and viscosity data<br />

from Riley and Skirrow ( 197 5). Diffusion co-<br />

efficients were calculated from equations given<br />

by Cussler (1984), Perry and Chilton (1973),<br />

and Dickson and Whitfield (198 1). Despite the<br />

large amount of information in the literature<br />

on scale formation in seawater, no experimental<br />

values for CaSO, diffusion coefficients in<br />

seawater could be located to compare with the<br />

computed values. At 25”C, the spread in the<br />

values of the difhtsion coefficients for the different<br />

salinities was on the order of 5%.<br />

Figure 9 compares our clod card data and<br />

those of Glenn and Doty (1992) with equations<br />

for spheres and flat plates. Glenn and Doty did<br />

not include a number of details relating to their<br />

clod cards and calibration conditions (e.g. block<br />

dimensions, water temperature, and salinity),<br />

so we did not use their data in obtaining Eq.<br />

9. With respect to other geometries, the clod<br />

card data are roughly the same magnitude as<br />

predicted by the sphere equation (Pasternak<br />

and Gauvin 1960), but the slope is different,<br />

possibly due to the presence of the mounting<br />

card. The flat-plate equation (Skelland 1974)<br />

parallels the clod card data but is substantially<br />

lower.<br />

Both Doty (197 1) and Muus (1968) expe-


1776<br />

Notes<br />

1000<br />

500<br />

< 200<br />

p 100<br />

7<br />

f 50<br />

3 Tap. ’<br />

v 20 30<br />

0 32 30<br />

b 40 “/.o<br />

0.5<br />

e- 0.4<br />

B<br />

z- 0.3<br />

P<br />

E<br />

6<br />

z<br />

0.2<br />

0 Baker (Tap, 30.3YZ)<br />

A EMS (Tap, 30.5’C)<br />

20<br />

f 0.1<br />

10<br />

200 500 1000 2000 5000 lE4 2E4 5E4 lE5<br />

Fig. 9. Comparison of clod card data with the equation<br />

of Pastemak and Gauvin (1960) for spheres (dashed line)<br />

and the equation for a flat plate (Skelland 1974), represented<br />

by the dotted line. The data of Glenn and Doty<br />

(1992) for 32960 seawater are shown, but were not used in<br />

obtaining Eq. 12. The points below iVRe = 1,000 are increased<br />

by natural convection and were also omitted from<br />

the correlation.<br />

NRI?<br />

rienced problems of variability of weight loss<br />

under uniform conditions by clod cards from<br />

the same batch. Referring to Fig. 2, the variability<br />

of clod card weight loss in our tests can<br />

be estimated by comparing the loss from<br />

matched pairs of cards at the same radial position<br />

on the arm (1, 2, 3, . . .) but on opposite<br />

sides of the arm. For all of our runs with<br />

EM Science plaster of paris at the different temperatures,<br />

salinities, and speeds, the standard<br />

deviation of the weight loss differences, as<br />

[CA w/KLIe* - (A IV/ WJsideZ], was 0.0135,<br />

while the overall average difference was 7.7 x<br />

10m4 (n = 60), which is not significantly different<br />

from zero (P = 0.05). Extreme variability<br />

of weight loss within a batch of cards<br />

caused no problems during our tests.<br />

We also ran limited tests with plaster of paris<br />

from Sargent-Welsh Chemical Co. (technical<br />

grade) and from Baker Scientific Co. (reagent,<br />

extra-fine powder ~44 pm, suitable for electrophoresis<br />

gel). The Sargent-Welsh material<br />

produced clod cards of the same density as the<br />

EM Science material used throughout these<br />

tests; a slight excess of water (375 ml : 500 g)<br />

used with the Sargent-Welsh plaster also failed<br />

to alter the final density. There was no significant<br />

difference between the dissolution rates<br />

of cards made with the Sargent-Welsh plaster<br />

and those made with EM Science material when<br />

tested under the same conditions. The cards<br />

made with plaster from Baker Scientific are of<br />

more interest because of their higher density:<br />

6 6 10 12<br />

Velocity, cm s -’<br />

2 5 1U LO<br />

Velocity, cm s -’<br />

Fig. 10. Effect of clod card density on dissolution rates.<br />

Cards made from reagent-grade plaster of paris from Baker<br />

had densities 50% higher than cards made with material<br />

from EMS. Upper plot illustrates differences in dissolution<br />

rates between the two batches, while the slopes of the lines<br />

in the lower plot of the same data, adjusted by the term<br />

Wi/Ai, are not significantly different (P > 0.05). Points<br />

below V = 2 cm s-l, influenced by free convection, were<br />

omitted from the analysis.<br />

1.8 g cm-3 as opposed to 1.2 for our standard<br />

EM Science material. High density cards are<br />

likely to be preferable for fieldwork because<br />

they take longer to dissolve than lower density<br />

cards of the same volume, and they tend to be<br />

stronger and less likely to be accidentally broken<br />

or chipped during handling. Figure 10 indicates<br />

that Eq. 8 holds for both high- and lowdensity<br />

cards when the proper values Of Ai/ Wi<br />

(1.38 for EMS and 0.92 cm* g-l for Baker) are<br />

used. Despite these results, one should use caution<br />

in changing the source or grade of plaster<br />

of paris; materials are occasionally added to<br />

building-grade material to lower the solubility<br />

and enhance water resistance.<br />

In addition to the rotating arm method for<br />

calibrating clod cards, we also wanted to pursue<br />

Doty’s (1971) and Howerton and Boyd’s<br />

(1992) suggestions for a free-convention meth-


od of calibrating that could be used in the field<br />

in the absence of the rotating arm apparatus.<br />

In quiescent solutions or solutions with very<br />

low forced convection rates, the density difference<br />

between the (saturated) liquid-solid interface<br />

and the bulk solution drives a convection<br />

current which is the principal mechanism<br />

that moves solution away from the solid. The<br />

natural and forced convection terms are in<br />

general not directly additive (Pei 1965; Churchill<br />

1977) in determining total convection or<br />

the dissolution rates.<br />

We suspended clod cards in quiescent solutions<br />

in ice chests under constant temperature<br />

conditions indoors. The ice chests supported<br />

dissolution rates roughly following Eq.<br />

4 over 4-6 d (Fig. 11A); Fig. 11 B correlates<br />

the natural convection ice-chest data. The<br />

equation fitting the data is<br />

[ 1 - ( W,lWi)1’3]/8<br />

= 2.81 ($)[(&)(+L.,,] 1.25 (10)<br />

with r = 0.994.<br />

Equations 8 and 10 can be combined to<br />

give an expression that will allow an equivalent<br />

integrated velocity to be determined from<br />

data obtained in the field. The group Sn =<br />

[ 1 - (~~ Wi)“]lB is obtained in natural convection<br />

clod card tests with water from the<br />

field test site. Weight loss data from cards exposed<br />

to water motion in the field is reduced<br />

to a corresponding form:<br />

Then the integrated<br />

calculated as<br />

Sf = [ 1 - ( Wr/ Wi)“]/8-<br />

water speed in the field is<br />

I/= 4.31(5=(y). (11)<br />

S’.25/Sn is similar to DF (Doty 197 1) but should<br />

be superior as an indicator of water motion in<br />

that it corrects for the effects of decreasing surface<br />

area during the tests and the greater effect<br />

of forced convection in producing dissolution<br />

relative to free convection (the 1.25 exponent<br />

for S&<br />

If field tests are conducted in water with lim-<br />

12<br />

'; 0.03<br />

0<br />

3<br />

?<br />

-y 0.02<br />

c<br />

r'<br />

Y<br />

C<br />

a ~0~/6.,25~C,n=Z<br />

. 25 3.. 16.5-C<br />

Time, d<br />

0.04<br />

, 0 Tap<br />

0 20 '/..<br />

0.01<br />

0.01<br />

0.02<br />

(T/T~~)&/P) AC250 mol Ihr-'<br />

A .<br />

Fig. 11. Free convection data obtained by suspending<br />

clod cards in large volumes of quiescent solutions in ice<br />

chests (A), and (B) correlation of the data using Eq. 8 at<br />

T,, = 298°K (25°C).<br />

ited motion, say V < 2 cm s-l, Eq. 11 will<br />

give erroneous results because free convection<br />

forces can also produce dissolution in the field.<br />

If it is necessary to separate the forced and free<br />

convection effects, multiply the right-hand side<br />

of Eq. 11 by [ 1 - (SJSf)3]5/12. This is a rough<br />

correction derived from Churchill (1977) for<br />

heat transfer with assisting forced and free convection.<br />

Many of the applications for clod cards involve<br />

measurement of unsteady flow, ranging<br />

from wind waves to oscillatory tidal currents.<br />

The methods presented here will indicate an<br />

integrated average speed near the scalar arithmetic<br />

mean velocity of the water because<br />

[ 1 - ( Wj &)“I/8 is nearly linear with velocity<br />

(actually Ve8). For example, if the water velocity<br />

over the card varies linearly from V, at<br />

time zero to V, at time 8, Eq. 1 and 2 can be<br />

used with the mass transfer coefficient from<br />

Eq. 8 to derive the expression<br />

0.03


1778 Notes<br />

Sample Points<br />

Along center Lines<br />

- 6.0<br />

- 5.0<br />

-4.0 h<br />

b<br />

E<br />

.2<br />

-3.0 .z<br />

2<br />

zi<br />

-2.0 z<br />

- 1.0<br />

ABCD<br />

0<br />

ABCD ABCD ABCD<br />

0.056 0.072 0.095<br />

Flow Rate (liters se’)<br />

Fig. 12. Water motion vs. flow rate in culture tanks. Clod cards were attached to metal bars inserted into tanks<br />

holding the cards in positions A-D indicated on insert drawing. Water source was freshwater at 30°C and weight loss<br />

of the cards was converted to water motion using the temperature-corrected curve for freshwater in Table 2. Line<br />

connects the mean value of water motion in each tank at each flow rate.<br />

ABCD<br />

0.160<br />

_- 0<br />

( )<br />

l/3<br />

l- 1-k:<br />

= o.74$-J(yf)<br />

x [ lv&;J$JACl~e. (12)<br />

The following is a numerical example: if<br />

speed varied linearly from 16 to 4 cm s-l<br />

(mean, 10 cm s-l) over a 24-h period in 25°C<br />

seawater with a salinity of 35Y&, then for a clod<br />

card with AJ Wi = 1.38 cm* g- l, the predicted<br />

fraction dissolved from Eq. 12 is A W/ Wi =<br />

0.328. From the steady flow Eq. 8, this dissolution<br />

fraction would be expected for a constant<br />

speed of 9.87 cm s- l, a value differing<br />

from the average flow in this example by<br />

- 1.3%. As previously explained, significant<br />

errors can be expected for low rates of water<br />

motion because the cards cannot differentiate<br />

between dissolution caused by free or forced<br />

convection under such conditions.<br />

The usefulness of clod cards in measuring<br />

natural and induced water motion was tested.<br />

In addition to the reef water motion experiments<br />

cited by Glenn and Doty (1992), the<br />

cards were used to investigate the amount of<br />

water motion induced by the flow of water into<br />

culture tanks (Fig. 12). Four cards were placed<br />

in the positions shown in each tank in order<br />

to measure water motion near the top and the<br />

bottom of the water column and at the outer<br />

circumference and near the center standpipe<br />

of the tanks (Fig. 12, insert). Increased flow<br />

into the tank mainly increased the amount of<br />

water motion near the periphery of the tank,<br />

whereas water motion near the center remained<br />

low. The results point up the inefficiency<br />

of using volumetric water exchange as<br />

a means of inducing water motion even though<br />

it is a common practice in culture studies.<br />

In conclusion, contrary to Muus (1968) and<br />

Doty (197 l), we have not found problems of<br />

erratic variability in fractional weight loss under<br />

seemingly uniform conditions by CaSO,<br />

blocks from the same lots. The still-water calibration<br />

method recommended by Doty (197 1)<br />

and Doty et al. (1986) should not be used. As<br />

pointed out by Howerton and Boyd (1992) as


Notes 1779<br />

well as Jokiel and Morrissey (1993), Doty used<br />

insufficient volume of bulk solution into which<br />

clod cards could dissolve. We recommend generating<br />

calibration curves for cards under forced<br />

convection conditions by using a rotating arm<br />

in a tank or a current meter. If a rotating arm<br />

in a tank is used, one must take into account<br />

the effect of induced water motion in the tank.<br />

Care must be taken that CaSO, does not accumulate<br />

in the tank; water should be changed<br />

every 2-3 runs if the tank is of limited volume.<br />

A standard curve relating water motion to<br />

clod card weight loss should accompany each<br />

report of a field study that uses the cards to<br />

quantify water motion. Water motion should<br />

be reported in velocity units under specified<br />

measurement conditions. Variations in temperature<br />

between field readings and standardization<br />

runs can be corrected using Fig. 4.<br />

In many instances, it is not possible to anticipate<br />

all conditions of temperature and water<br />

composition that may be encountered in<br />

the field; in such cases, Eq. 11 may allow a free<br />

convection test to be used to replace the forced<br />

convection calibration under field conditions.<br />

Freshwater produced lower dissolution rates<br />

than brackish or seawater (as expected on theoretical<br />

grounds), but over 20-40%, changes<br />

should be low. We do not anticipate large errors<br />

associated with water chemistry in practical<br />

applications of clod cards to marine systems.<br />

Although ice-cube trays were convenient<br />

molds, in theory a spherical shape would be<br />

more desirable because it would project the<br />

same surface area in all directions. Properly<br />

calibrated clod cards should find wide application<br />

in biological investigations in aquatic<br />

environments.<br />

Environmental Research Laboratory<br />

University of Arizona<br />

Tucson 85706-6985<br />

References<br />

T. Lewis Thompson<br />

Edward P. Glenn<br />

CHURCHILL, S. W. 1977. A comprehensive correlating<br />

equation for laminar, assisting, forced and free convection.<br />

AIChE J. 23: 10-l 6.<br />

CUSSLER, E. L. 1984. Diffusion: Mass transfer in fluid<br />

systems. Cambridge.<br />

DICKSON, A. G., AND M. WHITFIELD. 1981. An ion-as-<br />

sociation model for estimating acidity constants (at<br />

25°C and 1 atm. total pressure) in electrolyte mixtures<br />

related to seawater (ionic strength < 1 mole/kg H,O).<br />

Mar. Chem. 10: 315-333.<br />

Dorv, M. S. 1971. Measurement of water movement in<br />

reference to benthic algal growth. Bot. Mar. 14: 32-<br />

35.<br />

-, J. R. FISHER, E. K. ZABLACKIS, B. J. COOK, AND I.<br />

A. LEVINE. 1986. Experiments with Gracilaria in<br />

Hawaii, 1983-1985: A raw data tabulation. Univ.<br />

Hawaii Bot. Sci. Pap. 46. 486 p.<br />

GLENN, E. P., AND M. S. DO-I-Y. 1992. Water motion<br />

affects the growth rates of Kappaphycus alvarezii and<br />

related red seaweeds. Aquaculture 108: 233-246.<br />

HANSSON, I. 1973. A new set of pH-scales and standard<br />

buffers for sea water. Deep-Sea Res. 20: 479-491.<br />

HOWERTON, R. D., AND C. E. BOYD. 1992. Measurement<br />

of water circulation in ponds with gypsum blocks.<br />

Aquaculture Eng. 11: 141-155.<br />

JOIUEL, P. L., AND J. I. MORRISSEY. 1986. Influence of<br />

size on primary production in the reef coral Pocillopora<br />

damicornis and the macroalga Acanthophora spiczjka.<br />

Mar. Biol. 91: 15-26.<br />

-, AND -. 1993. Water motion on coral reefs:<br />

Evaluation of the clod card technique. Mar. Ecol. Prog.<br />

Ser. 93: 175-181.<br />

LAWS, E. A. 1975. The importance of respiration losses<br />

in controlling the size distribution of marine phytoplankton.<br />

Ecology 56: 419-426.<br />

MARSHALL, W. L., AND R. SLUSHER. 1968. Aqueous systems<br />

at high temperatures: Solubility to 200°C of calcium<br />

sulfate and its hydrates in sea water and saline<br />

water concentrates, and temperature-concentration<br />

limits. J. Chem. Eng. Data 13: 83-93.<br />

MATHIESON, A. C., E. T-R, M. DALY, AND J. HOWARD.<br />

1977. Marine algal ecology in a New Hampshire tidal<br />

rapid. Bot. Mar. 20: 277-290.<br />

Mws, B. J. 1968. Field measuring “exposure” by means<br />

of plaster balls-a preliminary account. Sarsia 34: 6 l-<br />

68.<br />

PASTERNAK, I. S., AND W. H. GAUVIN. 1960. Turbulent<br />

heat and mass transfer from stationary particles. Can.<br />

J. Chem. Eng. 38: 3542.<br />

PA-N, M. R. 1992. A mass transfer explanation of<br />

metabolic sealing relations in some aquatic invertebrates<br />

and algae. Science 255: 1421-1423.<br />

PEI, D. C. T. 1985. Heat transfer from spheres under<br />

combined forced and natural convection. Chem. Eng.<br />

Prog. Symp. Ser. 61: 57-63.<br />

PERRY, R. H., AND C. H. CHILTON [eds.]. 1973. Chemical<br />

engineers handbook, 5th ed. McGraw-Hill.<br />

REID, R. C., AND T. K. SHERWOOD. 1966. The properties<br />

of gases and liquids, 2nd ed. McGraw-Hill.<br />

RILEY, J. P., AND G. SKIRROW [eds.]. 1975. Chemical<br />

oceanography, 2nd ed. V. 1. Academic.<br />

SHERWOOD, T. K., R. L. PIGFORD, AND C. R. WILKE. 1975.<br />

Mass transfer. McGraw-Hill.<br />

SKELLAND, A. H. P. 1974. Diffusional mass transfer. Wiley.<br />

Submitted: 1.5 September 1993<br />

Accepted: 21 March 1994<br />

Amended: 19 April 1994

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