The Aquatic Safety of Neodol Products - InfoHouseinfohouse.p2ric.org/ref/27/26508.pdf · 2 INTIiODlJCTION NEODOL @products, composed of alcohols, alcobol eth0.aylate.s and alcohol

5 P??-+dt p dii7&/

THE AQUATIC SAFETY OF NEODOL@ PRODUCTS

SHELL CHEMICAL COMPANY

TABLE OF CONTENTS SECTION I , ,

-___-.___

2 ___-___ Introduction NEODOL@ Surfactants 2

~~ ~

Neodol Surfactants 2 Figure I 2

How Surfactants Affect Aquatic Life 2

5 Acute Testing, The LC,, 6 What It Is 6 How an LC,, is Determined 6

Table I 6 Table II 8 Figure 2 6, Figure 3 10

LC50 Limitations 10 Summary of Acute Effects 11 Alcohols 11

Ethoxylates 13 I 1 Figure 4

Figure 5 1.3 Figure G 14 Figure 7 14 Figure 8 15

Ethoxysulfates 16 General Trends 16

Figure I O 15

Summary 16 Chronic Testing 18

Table IV 19 Table V 19

Environmental Regulations 19 Table VI 20

Biodegradation -

_. -.”

Shell’s Commitment to Safety 20

2

INTIiODlJCTION NEODOL @products, composed of alcohols, alcobol eth0.aylate.s and alcohol ethoql.su!fate.s, are important cheinicak. for both home and industry

selues uuth the effects chemicals haue on man, spec& concerns such as aquatic toxicity are not as often addressed Shell Chemical Company &proud to prouide you with up-to-date information on our Neodol detergent products and their acute and chronic elfects in freshwater and marine environments. This infonnation includes the important area of biodegradabilicy

These data will show that Neodolproducts can be used safely and effectively uiiti~out adverse effects on the aquatic enuironment.

M9i.k we often concern our-

LEGEND - NEODOL 25-9 -- NBOI>OL 25-12

I I 0 5 10 15 20 25 30 35

EO GROUPS PER MOLE

NEODOL SURFACTANTS Surfactants (surface-active substances) in some form, usually 21s ingredients of detergents, are used by just about everybody, every da!: The), are found i n cos- metics, car washes, shampoos, dishwasliing powders, bubble baths, laundry products, and in household, industrial and institu- tional cleaners. Industry uses these products in metal working, paper and textile manufacturing, in formulating asphalt and pesti- cides, and as intermediates for chemical reactions.

find their way into the nation’s lakes, rivers, streanis and sewers.

Detergents in consumer products are commonly disposed of “down tlie drain,” usually end- ing up in tlie city’s wastewater. They then can I-,e decomposed by bacteria in a municipal wastewater treatment plant.

If there is no treatment plant or if the plant is incapable of breaking down all tlie detergent ingredients, these chemicals can be discharged into rivers, lakes, or oceans where they can possibly affect aquatic life.

Surfactants can also enter the environment indirect Iy from aqueous industrial effluents, run- offs from agricultural and asphal- tic uses or directly, by accidental spills during shipping and handling or from leaking storage

Once used, surfactants can

tanks located llear WaterWd\6. With these concerns in mind,

Shell Chemical Company has pre- pared this Imx-hure detailing aquatic safety data on tlie Neodol product line.

and designation for their linear alcohols, alcohol ethoxylates and et1ioxysulf:ites. DOBANOLE is the Neodol ec] i i i\den t product marketed by Shell International C h e ni i ca 1 C (1 ni pa n y, Ix n d (1 11,

These products :ire differen- ti:ited I-,!. ;I numbei- after [lie worcl Neoclol o r Ilobanol. The first two- digit numhcr refers t o (lie length

NEODOL is Shell’s trademark

o f the carhon chain o f the alcohol. The second numher gives the degree o f et1ios)kition.

For exanilde, Neodol 2 j refers to linear prini:ir>r alcohols with :I mixture of carbon c1i:iins with 13-15 carbon atoms. Neodol 25-7 is made up o f the same primary alcohols and is ethoqhted with an average o f seven moles of ethylene oxide (EO) per mole o f alcohol. It must be emphasized that this is the averagc number of moles of ethylene oxide and not the exact chemical descripiion. Tlie moles o f ethylene oxide per mole o f alcohol range from 0 to approximately 30 for Neodol 25-7. Other products have similar distribution curves depending on tlie average ethylene oxide con tent . (See Figure 1.for the EO distriix L- tion in two Neodolproducrs.)

Because each product con- tains only a slightly different range of molecules, tlie difference in the aquatic toxicities o f certain of these compounds will vary only slightly. Tlie toxicities of two Neodol products, for instance Neodol25-9 and tlie Neodol 2 5-12, should be very close because a good percentage o f the molecules in each o f these products are the same.

mental properties o f Neodol products will not var!, :is much as miglit be expected by just noting the difference i n product nomenclature.

For this reason, the environ-

HOW SURFACTANTS AFFECT AQUATIC LIFE A definite mode of action describ- ing the effect of nonionics on aquatic animals has yet to be determined. It appears, liowe\a-, that the observed effects in aquatic animals are caused b!- a conit-, ilia tion of ph!.sical and chemical fmors . One o f tlie most likel!. C:ILIS~S is (lie direct pli>.sic:il effect of the nonionic siirkict;int’s u.etting ahilit!.. ~

4

Wetting reduces w‘ ‘iter surface tension and causes disruption of membranes in the gill epithelium.1,2 This disrupts the exchange of gas and ions on the gill surface and adversely affects the animal’s respiratory function. The gill epithelium swells and secretes mucous, which further interrupts the diffusion of oxygen through the gill. The ultimate cause of death is suffocation, even in water that is saturated with oxygen.3

This effect would explain the data seen in Shell-sponsored

In concenthtionsslightly below LC,,, surfactants do not noticeubbj affect the

experiments on rainbow trout which revealed that fish do not

respiratory function of fish. In higher concentrations, anionics cause more dam- age to the@ structure than nonionics.

the chemical interaction hetween the gill epithelium and the surfactant molecule.

on the gill surface are emulsified by the surfactant while the gill membrane is penetrated by the hydrophobic portion (the alkyl

This causes a physical effect, an increase in membrane fluidity, which alters the mobility and the distribution of enzymes in the membra~ies.’.~ The gas exchange becomes less efficient, and the fish die of suffocation.

This hypothesis is consistent with the pattern seen in the accu- mulated data which shows that products with a longer ethoxylate chain are less toxic. A longer ethoxylate chain makes the molecule less fat soluble, thus hindering penetration into the gill membrane.

If interaction on the gill surface is one of the modes of action for surfactants, it would be consistent with the observation that active species are more susceptible to stress from exposure to these compounds. The species with the lower respiratory rate would pass less water and thus less surfactant over their gills. The

The natural mucus and oils

- exhibit mortality or stressful reactions in concentrations slightly below the LC,”’ (a derived number that represents the concentration of a chemical in water that will kill 50% of the test animals in a certain time. For more information on the LC,, see page 6).

A similar effect is exhibited by hydra, a fresh water coelenter- ate. The number of new buds formed by this animal was reduced in proportion to an increase in surfactant concentration until the level which disrupts cell membranes was reached, which had a lethal effect., These lethal concentrations always coin- cided with a surface tension o f approximately 49 dynes/cm.

Another mode o f action which probably contributes to the adverse effects of overexposure is

crustacean’s lower respiratory rate and thick cuticle around the gill epithelium would make this group more tolerant to high surfactant concentrations. This is apparently confirmed by the LC, values for these species.

with lipoproteins in membranes of nerve cells and eventually block portions of the nervous functions in the gill area.6

Anionics, although less acutely toxic, c;Iuse more perma- nent danYdge to the gill structure of fish than nonionics. Anionic surhctants form tighter salt coni- plexes with the proteins in the gill memlxane, resulting i n a loss o f respiratory function, TI1 is may explain the grcattr ability of fish t o recover after esposure to noti- ionic th:in t o anionic surfactants.

Surfactants may also associate

5

BIODEGRADATION Studies of linear alcohol ethoxylates have demonstrated that these substances rapidly and extensively biodegrade to harmless carbon dioxide and water.

Tests performed at Shell's Westhollow Research Laboratory in Houston and by the Shell Inter- national Chemical Company in England and the Netherlands have shown that Neodol type surfactants provide a carbon (energy) source for ambient bacteria in waterways and for the activated sludge in wastewater treatment plants.

Neodol products are rapidly and extensively biodegradable even at concentrations simulating spills (1,000 mg. per liter). With initial concentrations of 2 to 1,000 mg. per liter in shake flask tests (CO, evolution), it has been demonstrated that 70 to 80% of the Neodol ethoxylates biodegrade in three days.'

Radio-labeled experiments have indicated that the initial emymatic attack on Neodol ethoxylates occurs at the hydrophobe- hydrophile junction. This results in cleavage of the alkyl chain from the ethoxylate chainlo

The proposed mechanism for this primary biodegradation involves initial oxidative attack at the alpha carbon in the alkyl cluin of the Neodol molecule. This is followed by hydrolytic cleavage by an enzyme called an esterase which adds a fatty acid Coenzyme A derivative to the now separated hydrophobe portion."

cule, the alkyl and ethoxylate chains, are now available for further breakdown to CO, and H,O for utilization by microorganisms.

The two separated chains are then broken down metabolically by separate pathways. The alkyl is metabolized in the bacterial cell through an enzymatic process called lxta-oxidation. I 2 The process is similar to the metabolism of fatty acids. This metabolic path\vay oxidizes the alkyl chain at two car-

Both portions of the mole-

bon intervals toward the terminal methyl group.

The hydrophilic chain biode- grades into carbon dioxide and water by a different and presently unknown mechanism.

Shake flask experiments have shown that Neodol ethoxylates having up to 30 EO unitshole biodegrade at essentially equivalent rates. Biodegradation slowed con- siderably for Neodol ethoxylates containing 100 EO units/mole.9

At present, Shell only mar- kets Neodol products with a maximum of 13 moles of ethylene oxide per mole of alcohol (Neodol45-13). This is well within the ethoxylate range found to be readily biodegradable.

The following recent studies simulating "real world" situations have confirmed these general observations:

An activated sludge treatment plant in Ohio was dosed with 10 mg. per liter of Neodol45-7 under both summer and winter conditions. Samples taken throughout the treatment schedule indicated 90% primary biodegradation without any adverse effects on the treatment plant's performance.'3~~

Studies with Dobanol45-7 added to an activated sludge medium demonstrated rapid metabolism. Over two-thirds of the surfactant biodegraded within three days. Intermediate metabo- lites were not persistent and in ten days biodegradation was virtually complete. This was observed even though initial loading levels were high, simulating a spill situation or an accidental discharge from a manufacturing or formulating facility.lj

Abram et al. reported 96 to 98% primary biodegradation of Dobanol45-7 and 45-11 when loaded at 25 nig. per liter at the domestic waste treatment facility. This concentration is twice what nould be expected i n normal operations even under the most conservative conditions. Degrada- tion products in the effluent did

not have any apparent adverse effects on rainbow trout after a seven-day exposure.16

Another study showed 95 to 98% primary biodegradation of a similar product, Dobanol25-9, with an initial concentration of 20 mg. per liter. This was accom- plished even at temperatures down to eight degrees centigrade (46.4'Q.I'

biodegradation residues from the same product (Dobanol25-9) loaded at an initial concentration of 1,000 mg. per liter do not have any observable toxic effects on mosquito larvae, guppies, and a species of freshwater snail.I8

Laboratory simulated river die-away tests showed that a high initial loading of 20 mg. of primary alcohol ethoxylates per liter lost toxicity to rainbow trout in ten to 14 days."

Ileiff reported that Dobanol 45-7 biodegraded rapidly in river die-away tests with a subsequent loss of toxicity to rainbow trout.*O

In summary, laboratory and full scale field tests have shown Neodol products to break down rapidly to carbon dioxide and water in the environment. This breakdown results in a rapid loss of toxicity of these compounds to aquatic organisms.

Van Emden showed that the

6

ACLJTE TESTING, TIHE LC,, WI IAT IT IS. The Lethal Concentration-50% (LC,,,) is the statistically derived number that represents the concentration of chemical in the water that will kill 50% of the test animals in certain time. It is an acute (short-term) measure and does not addray chronic (long- term) efects. Aquatic toxicologists use it as the standard for comparing tlie relative acute toxicity of substances to aquatic animals and generally accept it as an early warning device about tlie potential effect of a substance on the aquatic environment. The LC5(, is a measure of lethality and as such should not he regarded as an enitironmentally acceptabk concentration. It merely represents the best estimate of the immediate impact on the aquatic enuiromnent

TABLEI

temperature, concentration o f the chemical, and length of exposure are all controlled.

Animals of a sensitive species in a larval or juvenile stage are often used in tlie test because of their greater sensitivity to stress. Fish such as bluegill sunfish, rainbow trout, goldfish and stickle- back are most commonly used.

water flea) are used extensively because of their great sensitivity to any change in the quality of the environment.

Saltwater (marine) species are also tested because pollutants can enter the oceans and estuaries directly from effluent discharges. The most sensitive life stages of these species, larvae and juveniles, as well as the less sensitive adult animals are tested. Common marine species that have been studied are the blue crab, hermit crab, brown shrimp, mussels and oysters.

on a sensitive population, the tests give a conservative estimate of the chemical’s effect on the aquatic environment. That is why it can be used to predict acute toxicity with some degree of confidence. Since the LC,, represents the value that will kill 50% of the individuals in the most sensitive life stage of a sensitive species, an environmen- tally “safe” concentration can then be estimated, but only for short- term exposures on aquatic life, most of which are less “sensitive” species.

When determining LC,,;s, the experimenter must always keep in mind that not all animals of the same species within a population group will respond in the same way. Some individuals wdl be more susceptible to the chemical’s effect and will die after a period o f time, even when exposed to low

Larval stages o f daplma (the

Since LC,,;s are determined

LC,,;s are determined on aquatic animals under experimental conditions where water quality

sometimes will show no signs of illness or distress. HOWAN LC, IS DETERMINED LC,ds are determined by exposing aquatic organisms to various concentrations of a chemical in tlie water. The number of deaths of the organisms are noted and 1) these data are statistically entered into equations, or 2 ) the deaths are plotted on a probit (or proba- bility) scale versus concentration on a logarithmic scale. This plotting technique makes the LC,, easy to estimate by observing the concentration that caused 50% mortality. Acute LC,,;s (short-term exposures) are estimated by two stages of experiments. The fit-st stage or “range finding” deter- mines the range of toxicity a compound may have on tlie aquatic organism. The second or “defini- tive” stage involves a series of tests to pinpoint a value that is closer to the actual toxicity.

give the experimenter guidelines for determining the concentrations to be used for the actual LC,,, tests. Only experiments can determine what concentrations will be lethal to some, but not all, of the test organisms. If test results pro- duce 0% or 100% mortality, an LC,, cannot be derived, either statistically or by plotting.

The range finding experiment is usually performed by adding a chemical in different concentrations to five tanks, each containing five of the test species. A sixth group of organisms, in a separate tank, acts as the control and is not exposed to the chemical.

Concentrations are increased by a factor of ten for each tank. After adding the chemical, the number of dead organisms are counted at a specific time interld, usually 24 hours. Tabk 1 shons sample data.

Range finding experiments

. dosages. Other, less susceptible animals will not only live, but

Uluegill Sunfish

8

loo[ 90

$ ~~~ 60

E 30

20

10

0 1 2 3 4 5

LC, Estimated at Approximately 4.0 mg/l

*O

CONCENTRATION ( m a )

FIGURE 2 Ewuvple Sanpk Plot-LC7,, Data. See Table !I

GENERAL TOXICITY DETERMINED BY MORTALITY COUNT &amble (Constunt Ratio Between Doses 1 8)

The data from this range finding test can then be applied to a 96-hour acute test for determining the LC,, of the chemical. For these data, the LC,, most probably lies between one and 10 mg. per liter. Knowing this, a 96-hour LC,, test can now be set up. Any number of concentrations can be used for this test, but a minimum should be four. For this test ten organisms are placed in each tank, the chemical is added, and the organisms are observed. Four or five different concentrations, each increasing in a geometrical (or logarithmic) progression, can usually give suf- ficient data for an accurate estimation of a chemical’s toxicity.

24,48, and 96 hours. The acute effects on aquatic life are most pronounced during the first 24 hours. Most of the signs of stress and the actual mortalities occur during this time. Thus LC,;s for 24 to 96 hours of exposure do not differ substantially within a species. Table N shows data for this theoretical chemical.

These data show the LC,, being narrowed down from 1-10 milligrams per liter to 3.2-5.8 milligrams per liter. Plotting the data on graph paper gives a better perspective.

Mortality counts are taken at

Figure 2 shows that the LC,, is approximately 4.0 mg/l for the example data. The technique of plotting deaths on a probit

a logarithmic scale is simply an extension of Figure 2. This plot will theoretically give an S-shaped curve with the point of inflec- tion at 50% mortality. Thus, the ‘‘straightest” part of the curve is at the 50% mortality mark.

probit plot. The 50% mortality (LC,,) estimated by this method is then 3.85 mg/l.

Several methods have been developed to calculate an LC,, statistically. One method, developed by C.S. Weil,2’ has the advantages of being fast and easy as well as accurate. Using this method, the LC,, for the sample data calculates to be 3.48 mg/l(95% confidence interval: 2.5-4.8 mg/l). Consider- ing the confidence interval, the log-probit plotting method is confirmed as being reliable.

The test described above is a “static” test. The water in these tests is not replaced. “Flow- through” or “frequent replace- ment” tests can also be run on aquatic organisms to establish an LC,,. As the name indicates, these tests are performed by continuall~~ replacing the water in the test chambers with fresh water con- tdlllillg the same concentration of

scale versus concentration on 3

Figzcre 3 illustrates a log-

the test substance. This allows tlie test animal to be exposed to a con- stant concentration of test substance thereby precluding the occuretice of toxic effects due to biodegradation products. Flow-through tests also remove such variables as volatilization and biodegradation from the final analysis.

times considered the counterpart to the LDio, which is used in mam- malian toxicology, there is a fun- damental difference between the two. The LD,, represents the dose administered to the test organism while the LC,, represents the concentration in the organism’s environment. The LC,, by itself does not indicate the dose the organism receives. Some organisms can accumulate concentrations of certain chemicals to potentially toxic levels while others may be resistant to tlie effects of those same chemicals.

Although the LC,,, is some-

100

< s o 80

70 i

60

50 10.685=3.85 mgil

11

30

20

10 - I ’,’ I

*--

I I

~- _+ -- __ --_

0 I I I .01 ,585 1.0

LOG OFCONCENTRATION

FIGURE3 Exam@? Sample Log-Prolm Plot-LC, Data: See TdAe I1

LC,;s are used in aquatic and inhalation tests. LD,,:s are most commonly used in oral, dermal and subcutaneous tests.

is also called an MTL or a median tolerance limit. An EC,, (Effective Concentration-50%) is the coli- centration that has a described effect on 50% of the test population. C‘suall!. an EC,,, IS used in cou tit i ng ” mi mo b ili zed” aquatic animals. 1

[In some publications, an LC,,

LC, LIMITATIONS

Although useful in establishing information on a chemical’s toxicity, the LC,, should be used only as a guide. It does not tell us all there is to know about a chemical’s toxicity to aquatic aninials.

Comparing data from different investigators is sometimes difficult since many laboratory techniques have not been stand- ardized. It is virtually impossible to simulate natural environment conditions in the laboratory. There are an infinite number of variable combinations that are continually changing in the environment. Many of these have an effect on tlie chemical’s toxicity to fish. Major considerations that can influence the chemical’s effect on aquatic animals include:

1. The temperature, salinity, and pH of the water as well as the age, sex, and overall health of the species and tlie species itself.

la) Active/Inactive Species- Active species appear to be more sensitive to the effects of surhctants than the inactive or sluggisli organisms. This is true for both fresli- water and marine species. For example, the bluegill sunfish and rainbow trout are more sensitive than goldfish. Hermit crabs can tolerate a very high concentration of surfactants in comparison to the free-swimming shrimp. lb) Larval Stages-Newly hatched aiid larval stages of aquatic animals are more sensitive than the eggs or adult stages. The tolerance of surfactants b~7 fish may increase slightly by slow acclimatization over a period of time.’,l IC) Aquatic Plants-Aquatic plants, algae, aiid bacteria are much less sensiti1.e to nonionic surfactants.22 2i This is significant because these pli!.- toplankton are considered to be the pimar!- producers o f

11

aquatic systems. Significant adverse effects on these organisms would have far- reaching effects on the aquatic ~ommunity.~’

2. The animal population itself can be a major source of varia- tion. Different populations of the same species may have ciif- ferent sensitivities. The time of year and the geographical location of the fish can also influence results. These variations have been known to affect the LC,, by one order of magnitude or more. 3. The LC,, is essentially a “knockdown” concentration. It reflects neither the recovery ability of animals exposed to the chemical,25 nor the chronic effects. 4. During laboratory tests the chemical concentration is either held COllStdnt by the experimenter or is slowlv decreased througli volatilization or decomposition because of bacterial metabolism. I n the environment, the chemical may vary in daily concentration, for example, near a sew- age or industrial plant efflu- uent discharge. 5. Adsorption of the surfactant onto organic matter can remove the chemical from the water, making it unaYailable to the animals in the environment. 6. Ecological s!.stems may be upset by tlie loss of a single sensitive species. 7. Species niay interact in an ecological system; one species metabolizing a chemical to a form more toxic to a second species. All combinations of species in an ecosystem are impossible to evaluate. 8. In evaluating the LC,, of a chemical, the sensitive species may not be selected for the test. Testing all species likely to be exposed is impossible. so choices depend on experiences with similar chemicals. This introduces uncert:iint)~ into

the value or meaningfulness of

Even with these considera- the LC,,.

tions the LC,, is a useful concept. The LC,, is generally accepted by aquatic biologists as a test that helps make a knowledgeable judgment on the risk of harm a chemical may have on aquatic animals.

DOBANOL 91

DOBANOL 23

DOBANOL 25

DOBANOL 45

LCw (mg/l)-96 hr. 0 10 20 30 40 50

I No Mortalilj at Saturation

SUMMARY OF-ACUTE EFFECTS The acute effects of Neodol products and other alcohol ethoxylates on the aquatic environment fall into distinct, predictable patterns. The different Neodol product lines (alcohols, ethoxylates, ethoxysulfates) show different toxicity ranges to aquatic life.

ALCOHOLS

These products decrease in toxicity as the number of carbon atoms in tlie alcohol increases. This is directly related to the alcohol’s water solubility. As the alcohol chain length increases, the water solubility decreases up to a point where the alcohol will simply float on the water surface. Toxicity

96 hour LC,;s for the alcohols range from 4 mg/l for the shorter chain Dobanol91 to a nontoxic ’

response at saturation for the longer chain product, Dobanol 45 (see Figure 4 ) .

studies reflect this phenom, pno11.

Dobanol is a Neodol elhcr\yhtes equit jaleiit, marketed by Shell Intertuuiondl Cfwniical Conipatq j, Loizdon.

13

ETHOXYLATES

As a general rule, when the EO chain length remains the same, an increase in the alkyl chain length increases the toxicity Conversely, when the alkyl chain length remains the same, an increase in the EO chain decreases the toxicity. The liposolubility (the degree to which a chemical will dissolve in a fatty-like material, i.e. gill epithelium) appears to be the largest Factor in determining the degree of lethality.6

Tests with rainbow trout, show a distinct decrease in tbxic- ity for Neodol and Dobanol etli- oxylates containing 14-15 carbon atoms as the degree of ethoxylation increased from seven to 18 moles per mole of alcohol (see Figure 5).

The reaction of goldfish (see Figure 6) and daphnia (see Figure 8) to a series of surfactants with fixed alcohol chains and increasing ethoxylate chains also shows this trend of decreasing toxicity.

This effect i s usually seen in nonionics containing alkyl chain lengths of 14 carbons or more and/or ethoxylation exceeding 14 moles per mole of alcohol. Non- ionics with less ethoxylation (i.e. 2-10 moles) are made of materials that are so similar that there is no significant difference between the toxicity of the products (see Figures 5 and 7).

a neat, observable trend (see Fg- ure 7), but the final results show differences which are still within an order of magnitude which is within the biological variability of these experimental designs.

Acute data for detergent range alcohol ethoxylates generally range between 1-5 mg/l for fresh water vertebrates. Products with higher ethoxylate content become less toxic with increasing hydrophobic chain lengths.

Crustaceans and other inver- tebrates (excluding daphnia) are very tolerant to alcohol ethoxylates, with most data showing LC,;s in the 500-5,000 mg/l range.

,

Other data do not show such

LC,, (mg/l)-96 hr.

0 1 2 3 4 5 6 7 8 9 10

DOBANOL 91-2.5

DOBANOL 91-5

DOBANOL 23-2

DOBANOL 25-3

DOBANOL 25-7

NEODOL 25-9

cl.2-14 € 0 8

Cl2.14 E010.6

NEODOL45-7

DOBANOL 45-11

DOBANOL45-18

ClS.ie €014

Tallow f:,

Alcohol EOl4

FIGURE 5 Summar?! of LC,S (96bt:) Rriinbou Trout Data: Appendix- I / @ 2)

Dobanol i s a Neodol ethoxyhtes equivalenl, inarketed @ Shell International Cf~emzcal Company, London.

NEODOL 23-6.5

NEODOL 25-3

NEODOL 25-9

NEODOL 25-9

Ci4.u EO9

Coconut Alcohol EO, I

I C ; < , (mgll)-96 111.

1 2 3 4 5 6 7 8 9 10 11 12 13

15

LC,, (nig/l)-96 hr.

0 10 20 30 40 50 60 70 80 90 100 110 iZ0 130 140

DOBANOL 91-2.5

DOBANOL 91-2.5s B NEODOL 25-39 - I NEODOL 25-3

Some marine species are not affected until very high coiicen- trations are reached. Lethal levels for tlie oyster range up to 20,000 mg/l and flat periwinkles can tolerate up to a 50% detergent and water mixture.

Daphnia, the most sensitive species used by aquatic toxicologists, has LC,(;s ranging from 0.3-2.0 mg/l for most tests.

TI-ie sulfation of the end EO group appears to reduce the acute toxicity of these compounds by a factor of 21-23 compared to the parent etlioxylate products. Ethoxysul- Fate Xi(, values generally range from 5-150 mg/l for freshwater fish <we Figure 9). GENERAL TRENDS The observable toxic effects on vertebrates overexposed t o nonionic surfactants run in tlie sequential pattern of increased activity, inactivation, immobiliza- tion and then death,L,L2Jj with an observable time lag between the first signs of stress and death.^"

The initial reaction, increased activity, is most probably an avoidance response and is characterized by exaggerated and erratic swimming. After a period of time the swimming rate is suppressed. The animal's equilibrium is affected and the fish experiences a loss of balance. Activity is then further suppressed as tlie fish becomes essentially immobi- lized in what appears to be an anesthetic or narcotic effect. If after this the fish is not removed quickly from exposure it will die.6

ET(IOX).WLI.;4TES

Acute effects on invertebrate species also show the classical loss o f swimming activity by the larval stage and a measurable reduction in growth rate if the exposure is over a longer period o f time.

if freshwater fish are removed from the test chainber and placed in clean water before they suc- cumb t o a lethal concentration, they frequent Iy recover.".LL.23 Th is is a Iso ti- ue for marine organ isms.

I n tests with tlie sensitive barnacle larvae, 50% of the organisms completely recover i n only 20 minutes after 30 minutes of

tion o f a nonionic surfactant. Con- versely, when barnacle larvae were given 30 minute exposures to the LC,,, of anionic and cat- ionic surfactants they Failed to recover any swimming act ivit !.

Experiments have shonn that

exposure t o the LC,,, concentra-

by the end of 48 hours.~, Tlius,'tlie ability for aquatic

animals t o recover completel!. after tlie surfactant is removed from tlie water is most prominent for the nonionic detergent class. This is significant because toxicity is most commonly measured using I,C,,;s (tlie "knockdown" concentration) and does not take into account the animal's ability to recover once exposure is reduced or eliminated. SUMMARY 1. Alcohols: They decrease in tox-

icicy a the number of cad7orz a t o m increases.

2 . Ethoxylates: When the EO chuin length remains the same, an increase in the alkyl chain length increases the toxic$ i

Converse&, when the alkyl chain remains the sume, un increase in the EO chain le) gth decreases the toxicity.

3. Ethoxysulfates: Thesulfatioil of the end EO group reduces the loxicity of these compounds by a.faclor of 21-23 compared to the parqzt etbouxylnre compound.

CHRONIC TESTING Unlike the acute test, which empha sizes finding the concentration that will theoretically kill 50% of the animal population in a short period of time, chronic tests are used to investigate the more subtle effects on the animal’s health, growth, and reproductive capacity over a long period of time. Like the results of acute tests, however, chronic test data should be viewed in light of testing conditions.

The highest test concentration with no effect on the animal’s health, growth or reproductive capacity during the full life cycle is called the Maximum Allowable Toxic Concentration (MATC) or the No Observable Effect Concen- tration (NOEC). The term NOEC is more descriptive of what has been measured and will be us6d in this publication.

Chronic tests usually last for the entire life cycle of the test animal; from the egg or juvenile stage through adulthood and into the juvenile stage of the next genera- tion. Chronic tests help determine the concentration that is “safe” for aquatic animals. The “safe” level, which is always lower than the

TABLE III

LC,,, allows for a normal life cycle. 50% of the animals are killed at the LC,, concentration level under laboratory conditions.

The most popular genus used for chronic testing is Daphnia, also known as the water flea. Daphnia have been used exten ,sively for chronic testing because of their ease in laboratory handling and short eight-day life cycle. Once a daphnia population has been started, they are relatively easy to grow, maintain, handle and count. I n a well main- tained culture, enough daphnia are produced to perform daily toxicity tests. The number of animals produced is large enough to allow a good statistical correlation of data. This is important because the more animals that are tested, the better the confidence level of the test results. Two daphnia species are used for aquatic testing: Daphnia magna and Daphnia pukx. No significant difference between the two species has been found in regard to their reaction to chemicals in the water.z7

Another popular choice for chronic testing has been the fathead milinow because it has little trouble reproducing under iabo- ratory conditions, is easy to hdn- dle and has a relatively short life cycle (10-12 months).

There has been limited chronic testingpei:formed with alcohol ethoqdates. Long-term exposure to low levels of alcohol ethoxylates in continuous flow tests has been shown to deci-eaw the respiratory rate in fathead minnows. The decrease was directly related to test concentrations. Respiratory rates, licxvever, were incrcawd on exposure to alcohol ethoxysulfates.zx

The mode of action for this change in respiratory rates is unclear, (see Tuble III) but it may be related to a chemoreceptor function in the gills.

19

Chronic tests on the effects of ethoxylated tallow alcohols (average of 10 moles ethylene oxide per mole of alcohol) on the fertilization and spawning of mussels have s1ion.n that spawning ability was not affected at concentrations as high as 1.5 mg/l. These tests lasted f i i re months. Fertil- ization rates, however, were decreased b!. increasing the tallow alcohol ethoy-late concentrations. Almost complete inhibition o f egg fertilization was seen at the 2.0 mg/l 1e~el.l~

Recent data show that nonionic surfactants are readily taken up by bluegill sunfish and goldfish, but an analysis of individual organs indicates that most of the product is found in the gall blad- der. The rnuscle tissue showed the least concentration of surfactant.L’

Tests to determine the NOEC on estuarine organisms reveal that this type of organism can live in water without an observable effect u p to 72% o f the LC,,, concentration-”’ &e Table IV).

This high NOECLC,, ratio confirms the steep dose-response curve seen during acute testing and adds evidence to the hypothesis that acute effects become evi- dent when the surface tension of the water is reduced to a particular level.

Studies comparing daphnia and fathead minnow NOEC values have shown that these species are also capable of lilring without adverse effect in water with coli- centrations of alcohol ethoxylates approaching the LC,, ~ a l u e 3 ~ (see Table V).

This study not onlp indicates that relativel>- high ambient coli- centrations of surfactants can be tolerated nithout adverse effects, but also s1ion.s the high absolute value tolerated b y daphnia, one o f the most sensith-e species used b y aquatic toxicologists.

SPILL. SITIJAT IONS Direct spills o f alcohol ethoxylates into waterways are different from environmental run-offs. For more details, see Appendix IY

ENVIRONMENTAL REGULATIONS CLEAN WATER ACT (CWA)

.Neodol alcohols and derivatives are not hazardous substances as defined by the Clean Water Act regulations.

RESOURCE CONSERVATION AND RECOVERY ACT (RCRA) As manufactured and supplied to our customers, Neodol alcohols and detergent products are not classified as hazardous wastes as defined by RCRA regulations.

7.W4HLE I v

MINNOW AND DAPIINIA-NOEC

TABLE V

20

TOXIC SUI3STANCES CONTROL ACT (TSCA) As required by law, Neodol alcohols, alcohol ethoxylates and alcohol ethoqsulfates are listed on the Toxic Substances Control Act Inventory: (see Tuble VI below)

?ABLE VI

SHELL’S COMMITMENT TO SAFETY This publication represents another integral part of Shell’s commitment to safety and is one of the many available on the environmental safety and safe handling of Neodol products. MATERIAL SAEETYDATA SHEETS (MSDS) For Material Safety Data Sheets on all current Neodol products, write: Shell Oil Company One Shell Plaza Health, Safety and Environment PO. Box 4320 Houston, Texas 77210

will be put on a mailing list and will automatically be mailed revised MSDSS when any new and significant safety or toxicology information is added. SHELL CHEMICAL SMETYGUIDE

Customers receiving MSDS’s

The new Shell Chemical Safety Guide lists many of our chemical products including the Neodol alcohol detergent product lines. The safe-handling guidelines are accompanied by illustrations in this handy, easy-to-read pocket- sized booklet.

BIOUEGRADATION STUDIES Technical bulletins on the biodegradation studies performed at Shell’s Westhollow Research Cen- ter in Houston are also available. These publications detail tests showing Neodol products’ ultimate biodegradation properties.

on the toxicology, proper hati- dling, storage and environmental aspects of Neodol alcohols and detergent products are available at Shell’s Regional Sales Offices.

These publications and others

THE AQUATIC SAFETY OF NEODOLO PRODUCTS

SUP P LEM E NTA KY 1 NFORM AT ION

TABLE OF CONTENTS SECTION IP

Appendix I 2 Summary of Common andScient@c Names for Aquatic Est @Ranisms

Appendix I1 Summary of Raw Data @Species Rainbow Trout Goldfish Sluegill Sunfish Daphnia Channel Catjfiib G*&V Blue Crab Harlequin Fish Hermit Crab Fathead Minnow Shore Crab Oyster Golden @fe Brown S h i m

2

2 2 3 3 3 3 .? 3 3 4 4 4 4 4

Appendix I11 5 Summurv of Raw Data by Chemical

Alcohols 5 C&, , Alcohol Ethoxylates 5 C,,-C,, Alcohol Ethoxvlates 5 C,,-C,, Alcohol Ethoxylates 6-7 C,,-C,, Alcohol Ethowlates 8-9 C,,-C,, Alcohol Ethoxylates 10 Sulfated Alcohols and Ethoxylates 10 Other 11 Appendix IV

Spill Situations 12

%ill Situations 12 Analysis of the Situation 12 Action in Spill Situations 12 Kemoving the Source 12

Control of the Spill 13 Sampling the Spill Area 14 Safety Information for

Neodol Products 14 Shipping DaWStorage and Handling 15 General Bibliography 16

DOBANOL 25-7 2.7 NEODOL 25-9 1.2

C,,.I4EO, 0.8

No Significant Dgferences

2

APPENDIX I

SUMMARY OF COMMON AND SCIENTIFIC NAMES FOR AQUATIC TEST ORGANISMS ~~

COMMON NAME GENUS AND SPECIES COMMON NAME GENUS AND SPECIES

Atlantic Salmon Salmo salar Fathead Minnow P i r n e p l J u ~ . ~ p r o ~ ~ e l ~ ~ Flat Periwinkles Litfornia spp. (or similar) Barnacle Elminius modestus

Bluegill Sunfish Lepomis macrochirus Channel Catfish Ictalurus bU~CtatUS

Flounder Pleuronectes flesus Golden Orfe Idus idus melonotus Goldfish caiakius auratus Clam Mya arenariu

Cockle Cardium edule Codfish Gadus motrhua

GUDDV Poecilia reticukata ~~ ~~

Harlequin Fish Rasbora heteromorpha Hvdra Hlidru attenuafa

~

Crab, Blue Ca flinectes sapidus Minnow Phoxinus bhoxinus

~ ~~

Crab, Hermit Eqagurus bernhardus ~

Mummichog Fundulus hereroclitus Mussel Myfilifi edufis

Crab. Shore Carcinus maenus Crab, Spider Hyas araneus Crustaceans Balanus balanoides

Leander adspeaus Leander squilla

Dabhnia Pulex Daphnia Daphnia magna

Oyster Ostreu edulis

Rainbow Trout Salmo gairdneri Shrimtx Brown Cranpon cranpon

Crassostrea virginica

Shrimp, Pink Penaeus duorarum

APPENDIX II

SUMMARY OFRAWDATA BYSPECIES RAINBOW TROUT CHEMICAL 96 HOUR LCw (mg/l)

DOBANOL* 91-2.5 5-7 DOBANOL 91-2.5s 130-147 DOBANOL 91-5 8-9 DOBANOL 23-2 DOBANOL 235-3 DOBANOL 25-3

GOLDFISH

CHEMICAL LC, (mrr/l)

Cl2EO4 5.2 (6 hrs.) Ci ,EO, 1.9 (48 hrs.) C, .EO, 8.5 (6 hrs.) C1%14E06 3 1.4 (24 hrs.) C12-14E0, 4 1.8 (48 hrs.)

1.8 (6 hrs.) 1.4 (48 hrs.)

cl 2-1 4E08

4.3 (6 hrs.) 3.0 (48 hrs.)

Tallow Alcohol EO14

C, Alcohol 2 E 0

7.9 (6 hrs.) 2.1 (48 hrs.) 2 ( 1 hr.) 0.8-1.8 1

NEODOL 45-7 0.9

DOBANOL 45-18 5.0-6.3 C16 ,,EO14 0.8 (24-hr)

DOBANOL 45-1 1 1.8-2.5 C,, Alcohol 4E0 4 (1 hr.) C,, Alcohol 6EO C, Alcohol 8E0

5 (1 hr.1 7 (1 hr.)

C,, Alcohol lOEO 10 (1 hr.) Tallow Alcohol EO,, 0.4 DOBANOL 91 6-10 DOBANOL 23 4-10 DOBANOL 25 45 DOHANOL 45 ,\,o i?iormli/>i iipon

.tat1 /ra//(x1

C,, Alcohol 12EO C,, Alcohol 14EO

20 (1 hr.) 30 (1 hr.1

C,, Alcohol 16EO 40 ( 1 hr.) C,, Alcohol 18EO 100 (1 hr.) C,, Alcohol 20E0 - 110(1 hr.)

I - _ U.) I - ~~

1’23 ClZ-13E06 5 1.14 C12-14E06 3 1.5

NEODOL 25-9 No Significant Differences

3

APPENDIX II

BLUEGILL SUNFISH

CHEMICAL 96 HOUR LC,, f m d )

HARLEQUIN FISH

CHEMICAL 96 HOUR LC, (me/l\ ~~~~

NEODOL23-6.5 2.0-2.4 NEODOL 25-3 1.5

DOBANOL 25-3 (30% Kerosene) <10

NEODOL 25-33 32 C,,.*,EOR 1.2 (48 hrs.) -~ NEODOL 25-9 1.9-2.1 NEODOL 25-9 7.8

~

Clz-l4EOlo 5 1.6-2.8 DOBANOL 45-1 (30% Kerosene) 30 DOBANOL 45-1 (30% IPA) 80

i

C14-18E09 10.0 Coconut Alcohol EO, 12.3

DAPHNIA

CHEMICAL 96 HOUR LC,, (mg/l) NEODOL23-6.5 , 0.901

~~

DOBANOL 45-3 (30% IPA) 5 &EO, (30% IPA) >2000

~~

Tallow Alcohol EO,, 0.7 Coconut Alcohol EO, 10-100 (48 hrs.)

HERMIT CRAB

CHEMICAL 48 HOUR LCw (mg/l)

DOBANOL 25-3 1000-6000 (6 hrs.) (30% Kerosene) 85 (48 hrs.) C14-15E07 0.431

Cl4EOl 0.8 Ci4EOz 1.5 C14E03 0.7 C,,EO, 1.8

~

DOBANOL 45-1

DOBANOL 45-3

DOBANOL 45-1 1

C,,EO, (30% IPA) <<loo0

(30% Kerosene) 3000-6000

(30% Kerosene) <2000

(30% Kerosene) >640 (6 hrs.) ._ . .

C&O, (30% IPA) <loo0 ClzE09 (30% IPA) <<loo0

CHANNEL CATFISH

CHEMICAL 96 HOUR LCw (mg/l) NEODOL 25-9 1 2 DOBANOL 45-1 (30% IPA) 3000 _ . - .- NEODOL 25-12 1.8 DOBANOL 45-3 (30% IPA) <loo0

C,,EO, (30% IPA) 4000 GUPPY

CHEMICAL 96 HOUR LC, (mg/l) DOBANOL 25-3 (30% IPA) 50

CI~EO, (30% IPA) 1500 Ci&O, (30% IPA) 2500

_ -

CiziJQ (34% HZO) 3.2-10.0 DOBANOL 45-1 (30% Kerosene) 60

~

C&O, (30% IPA) 3500 CI6EO9 (30% IPA) 2000

DOBANOL 45-1 (30% IPA) 100-1000 DOBANOL 45-3 (30% IPA) 10 CI,EOl(30% IPA) >loo0 C16E014 0.7 (24 hrs.)

1500-4000 ~

4000 4000

~

DOBANOL 25-9 (30% IPA)

(30% Monoethylene Glvcol Solution) >5000 (6 hrs.)

>640 (6 hrs.) DOBANOL 25-9

BLUE CRAB -~

CHEMICAL 96 HOUR LC, (mg/l) Tallow Alcohol EO,,, >lo0 (96 hrs.)

s

._ ..:~ .. .

4

APPENDIX II

FATHEAD MINNOW GOLDEN OWE

CHGICAL 96 HOUR LC,, (mg/l)

NEODOL 25-9 1.6 _ _ NEODOL 25-12 3.6 C12-14E06.3 1.8 (24 hrs.) C1*.14EO7.4 1.8 (24 hrs.)

SHORE CRAB CHEMICAL 6 HOUR LC,, (mg/l)

DOBANOL 25-9 >640 DOBANOL 25-9 >5,000

(30% Monoethylene Glycol Solution)

DOBANOL 25-9 (30% IPA) > 5,000 DOBANOL 45-1 1

DOBANOL 45-11 (30% IPA)

>640 (6 hrs.)

> 5.000 (30% Kerosene)

OYSTER CHEMICAL 6 HOUR LC, (mg/l)

CI,,EO7 (larvae) 0.11 (48 hrs.) DOBANOL 25-9 20,000 DOBANOL 25-9 >5,000

(30% Monoethylene Glycol Solution)

DOBANOL 25-9 (30% IPA) DOBANOL 45-11 (30% Kerosene) >640

> 5,000

96 HOUR LCx, (mg/l) CHEMICAL

C, 7.1 LEO, 1.8-2.7 C12-14E010.5 4.1-4.5 C12-14E011 2.7 (48 hrs.) Tallow Alcohol EO,, 2.3-2.5

BROWN SHRIMP

CHEMICAL 48 HOUR LC, (ma'l) ,". - I -~ ~ ~

DOBANOL 25-3 (30% Kerosene) 20-300 DOBANOL 45-3 (30% Kerosene) 50 DOBANOL 25-3 (30% IPA) 200 DOBANOL 25-9 >3,300 DOBANOL 45-1 500 DOBANOL 45-1 200 _ - - -~~~ ~

DOBANOL 45-1 1 3,300 (6 hrs.)

DOBANOL 45-11 (30% IPA) > 5,000

5 APPENDIX 111

SUMMARY OF RAWDATA BY CHEMICAL ALCOHOLS,

LC% (" CHEMICAL SPECIES 24 HR 48 HR 96 HR. REF NO

DOBANOL 91 Rainbow Trout - 6-10 6-10 32 4-10 33 DOBANOL 23 Rainbow Trout - -

DOBANOL 23 Goldfish Non-toxic at saturation. 34

DOBANOL 25 Rainbow Trout - 68 45 35 (2.4 mg/l)

DOBANOL 25 Goldfish Non-toxic at saturation. 34

DOBANOL 45 Rainbow Trout N o mortality upon saturation. 36 (0.8 mg/l)

DOBANOL 45 Goldfish Non-toxic at saturation. 34 (0.7 mg/l)

G-CI, ALCOHOL ETHOXYLATES

LCW i" CHEMICAL SPECIES 24 HR. 48 HR. 96 HR. REE NO.

DOBANOL 91-2.5 Rainbow Trout - 5-7 5-7 37 DOBANOL 91 -5 Rainbow Trout - 8-9 8-9 38

25 - - C,, Alcohol 20E0 Barnacle 5.6 x 1 0 - 4 ~ * (Stage I1 larvae)

'30 Minute EC, "Immobiizly"

CI,& ALCOHOL ETHOXYLATES

LC%(" CHEMICAL SPECIES 24 HR. 48 HR. 96 HR REE NO

1-2 1-2 39 DOBANOL 23-2 Rainbow Trout - NEODOL23-6.5 Bluegill Sunfish 2.45 - 2.36 7

1.6** NEODOL23-6.5 Daphnia 1.05 - 0.90 7 NEODOL23-6.5 Bluegill Sunfish 2.36 - 2.05 7 NEODOL23-6.5 Daohnia 0.57 - 0.57 7 DOBANOL 235-3 Rainbow Trout - 1.0 1 .o 40 *'No Eflcct Lael

APPENDIX 111

C,,-C,, ALCOHOL ETHOXYLATES

CHEMICAL SPECIES 24 HR 48 HR. 96 HR. LCw (mg/l)

REF. NO.

NEODOL 25-3 Bluegill Sunfish 1.8 - 1.5 41 DOBANOL 25-3 Rainbow Trout - 1.3-1.7 1.3-1.7 42 DOBANOL 25-3 (30%) Harlequin Fish 10-30(2 hr.) - <10 43 (?&"e Solution) GUPPY 300-1,000(2 hr.) - 30-100 43

DOBANOL 25-3 (30%) Harlequin Fish - - < l o 8 CKemreneSolution) GUDDV - 50 8 -

8

43 43 43 8

- 85 DOBANOL 25-3 (30%) Hermit Crab - (Kerosene SOluhOrt)

DOBANOL 25-3 (30%) Brown Shrimp - 20-300 - (Kerosene Solution) Hermit Crab 1,000-6,000( 6 hr.) 85

Flat Periwinkle 500,000( 1 hr.) - DOBANOL 25-3 (30%) , Brown Shrimp - 200

DOBANOL 25-7 Rainbow Trout - - 2.7 22 Channel Catfish 1.4 - 1.2 44 Fathead Minnow 1.6 - 1.6 44 Rainbow Trout 1.6 - 1.2 44

NEODOL 25-9 Bluegill Sunfish 1.87 - 1.86 7

- - -

@opqxnwlSoluhon)

NEODOL 25-9

1.4** NEODOL 25-9 Bluegill Sunfish 2.1 - 2.1 41

41 (static)

(dynamic) Bluegill Sunfish 2.7 - 2.1

NEODOL 25-9 Bluegill Sunfish 8.0 8.0 7.8 45 0 5 % l i m n r t m a r v )

1 _I, . - NEODOL 25-9 Bluegill Sunfish 11.0 11.0 11.0 45 -

(98% 1inearpflmat-y)

DOBANOL 25-9 (30%) Brown Shrimp - >3,300 - 46 (lsoprqanol Solmbn)

NEODOL 25-9 Daphnia 1.71 - 1.23 7 DOBANOL 25-9 Hermit Crab >640*(6 hr.) -

Shore Crab >640*(6 hr.) - Oyster >20,000*(6 hr. j - -

DOBANOL 25-9 (30%) Hermit Crab > 5,000*(6 hr.) - - (Water and Monoetbykwe Shore Crab > 5,000*(6 hr.) -

Ovster >5.000*(6 hr.) - -

- 46 - 46

46 46

- 46 46

Glycol Solurron)

46 46

DOBANOL 25-9 (30%) Shore Crab > 5,000*( 6 hr.) - - (Waterand Oyster > 5,000*(6 hr.) - - Isopropanol Solution)

~~~~ ~

NONIDET SH (34%) Harlequin Fish (CiZ.,, AlC&l 3EO) GUDDV

1-3.6 i-3.6 1-3.6 47 3.2-10 3.2-10 3.2-10 47

NEODOL 25-12 Channel Catfish 2.1 - 1.8 44 Fathead Minnow 3.7 - 3.6 44

- 48 C,, Alcohol 2E0 Goldfish 2( Ihr. j - - 48 C,, Alcohol 4 E 0 Goldfish 4( 1 hr.) -

*5 Day Obseriation '*No gfect L e w l

4

APPENDIX 111

LC, (mg/l) CHEMICAL SPECIES 24 HR. 48 HR. 96 HR. REF NO.

48 48

- 48

C,, Alcohol 6EO Goldfish 5(1 hr.) - - C,, Alcohol 8EO Goldfish 7( 1 hr.) - - c17 Alcohol lOEO Goldfish lO(1 hr.) - c17 Alcohol 12EO Goldfish 20(lhr.) -

48 C,, Alcohol 14E0 Goldfish 30(lhr.) - - 48 48 48 49 50 37 22

Fathead Minnow 1.8 - 22

C,, Alcohol 16EO Goldfish 40( 1 hr.) - - C,, Alcohol 18 EO Goldfish 100( 1 hr.) - - C,, Alcohol 20EO Goldfish llO(1hr.) - - C,, Alcohol 4 E 0 Goldfish 5.2(6 hr.) - - C,, Alcohol 9E0 Goldfish - C13 Alcohol 5 E 0 Goldfish 8.5(6 hr.) - -

- 1.9

- - c12-14 Alcohol 6.3EO Goldfish 1.4 -

- 22 Fathead Minnow 1.8 - 22

31 1.14 31 Daphnia - - .

0.93 (21 Days) 31 31 Daphnia 0.24(NOEC) - -

C,,,, Alcohol 6.3EO Daphnia 2.5 2.4 1.5 22 22 51 C12.14 Alcohol 8E0 Goldfish 1.8(6 hr.) 1.4 - 51 Harlequin Fish - 1.2 -

0.25-1.0 0.8 51 Rainbow Trout - 2.7 2.7 51 Golden Orfe - 1.8 1.8 51 Golden Orfe -

51 Harlequin Fish - 1.6-2.8 1.6-2.8 51

2.5 1.8 51 Rainbow Trout - 1.2 0.8 51 Rainbow Trout - 4.5 4.1 51 Golden Orfe - 4.6 4.5 51 Golden Orfe -

22 22 22 44

8

8

22

c12.14 Alcohol 7.4EO Goldfish 1.4 - - - - C12.13 Alcohol 6.5EO Fathead Minnow 0.32( NOEC)

- - c12.14 Alcohol 7.4EO Daphnia 2.3

C,,.,, Alcohol 10.5EO Goldfish 4.3(6 hr.) 3.0 -

C12.14 Alcohol l lEO Rainbow Trout 6.2 6.2 - C12.14 Alcohol 11EO Golden Orfe - 2.7 - Cl2.14 Alcohol l lEO Daphnia 5.1 C,, Alcohol 1EO (30%) Hermit Crab - << 1,000* - CI2 Alcohol 3E0 (30%) Hermit Crab - < 1 ,ooo* -

C12Alcoho19E0 (30%) Hermit Crab - < < 1 ,ooo* -

C,, Alcohol 14EO Daphnia 1.1

.- -

(Isq6ropanol Solutaon)

(Isoprqmtwl Solution)

(Isopropanol Solutron) - -

'5 Day Observation

. . . -. . . .

8 APPENDIX 111


CHEMICAL SPECIES G o ("

24 HR. 48 HR. 96 HR. REE NO

DOBANOL 45-1(30%) Harlequin Fish (Isopropanol Solution) G ~ P P ~

30 8 60 8

8

(Kerosene Solution) Harlequin Fish - - - - Guppy

DOBANOL 45-1 (30%) Hermit Crab - 3,000* - (Isomwan01 Solution)

8 8

(Kerarene Solution) Hermit Crab - 3,000-6,000* - DOBANOL 45-1 (30%) Brown Shrimp - 500* -

(Isopropanol Solution)

DOBANOL 45-3 (30%) Harlequin Fish GUPPY Hermit Crab Brown Shrimt,

(Isopropanol Solution) 5 8

10 8 8 8

- - - -

- < 1 ,ooo* - 200* - -

8 8

23

ocemM?e Solution) Hermit Crab - < 2 ,ooo* -

NEODOL 45-7 Bluegill Sunfish - 0.66 - - 50* Brown Shrimp -

NEODOL 45-7 Fathead Minnow (Tap Water) 0.8** - (Creek Water) 0.8** - (2nd Effluent) 2.0** -

1.2 27 1.4 27 2.5 27

52 52

1.05 0.96 0.90 52

DOBANOL 45-7 Rainbow Trout 1.75(8 hr.) - - - , 1.20(12 hr.) -

0.9 0.8(4 day) 26 - 0.7(7 day) 26

Rainbow Trout 1.5 (water) - (effluent) 1.2 1.1 0.8(4 day) 26

- - 0.5(7 day) 26 NEODOL 45-7 Daphnia magna

23 (35maN hardness) DaDbnia mama - 0.34 - 23 23

ClBlmgII hardness) Daphnia magna - 0.29 -

(340mKIlhardness) Daphnia magna - 0.40 - NEODOL 45-7 Daphnia magna

23 23 23 23

(25mgfl hardness) Daphnia magna - 0.36 - (125mgflbardness) Daphnia m a g m - 0.34 -

- (225mgll bardnes) Daphnia magna - 0 40 (3225md hardma) Dabbnia mamu - 0.38 -

0 - _ - DOBANOL 45-1 1 Rainbow Trout - 1.8-2.5 1.8-2.5 52 DOBANOL 45-1 1 Rainbow Trout

(water) (effluent)

1.5 1.1 ~ ( 4 day) 26 - - LO(7 day) 26 1.3 1.2 1.1(4 day) 26 - - 1.0(7 dav) 26

'5 D q 0bseri:ation "NO Eflect L a d

9 APPENDIX 111

L I

CHEMICAL SPECIES LCw (mg/l)

24 HR. 48 HR. 96 HR. REF. NO.

- 46 46 46

DOBANOL 45-11 (30%) Hermit Crab >640*(6 hr.) - &mse”seneolwiOn) Shore Crab >640*(6 hr.) - -

Ovster >20,000*(6 hr.) - -

46 - 46

46

DOBANOL 45-11 (30%) Shore Crab > 5,000*(6 hr. ) - -

Brown Shrimo - 3,300*(6 hr.) - [Iscpmpanol Solution) Oyster > 5,000*(6 hr.) -

DOBANOL 45-18 Rainbow Trout - 5.0-6.3 5.0-6.3 53 CI4 Alcohol 1EO (30%) Harlequin Fish - - >2,000 8

(Isoprqbnol Solution) GUDDV - - > 1,000 8 8 C14Alcohol 1EO (30%) Hermit Crab - 4,000* -

C,, Alcohol 3 E 0 ASTM 1345-59 - - 3(4 dav) 54 (I-wnool Solution)

8

6 3.5 2.7 1.5 6

c14 Alcohol 3 E 0 (30%) Hermit Crab - 1,500* -

C,, Alcohol 4E0 Atlantic Salmon 2.2 (IsopppanolSolution)

- -

22 22

- C,, Alcohol 8E0 Rainbow Trout 2.5 2.4 C,, Alcohol 8 E 0 Golden Orfe 1 .o - - C,, Alcohol 8EO ASTM 1345-59 - - 3(4 dav) 54

22 - - CI4 Alcohol 8E0 Daphnia 2.0 Cl,,, Alcohol 9E0 Bluegill Sunfish 10.0 10.0 % 10.0 45 CI4Alcohol9EO (30%) Hermit Crab

Osoao~anol Solution) 8 - 2,500* -

C14 Alcohol 15EO ASTM 1345-59 - - 5(4 day) 54 C,, Alcohol 24E0 ASTM 1345-59 - - 30(4 dav) 54

31 Daphnia 0.24(NOEC) - 0.43 31

- 0.37(21 day) 31

C14.15 Alcohol 7E0 Fathead Minnow 0.18( NOEC) - -

- 0.78 30

(0.34-1.8) 30 CI4 Alcohol 7 E 0 Pink Shrimp 0.56( N OEC) -

Blue Crab 1 O.O( NOEC) - 30.9 (26.2-36.5)

1.45 30 56

Mummichog 1 .O(NOEC) - C14 Alcohol 1EO Daphnia magna - 0.83 -

56 C14 Alcohol 2E0 Daphnia magma _I 1.53 -

56 56

C14 Alcohol 3E0 Daphnia magna - 0.73 - CI4 Alcohol 4 E 0 Daphnia magna - 1.76 -

56 56

C,, Alcohol GEO Daphnia magna - 4.17 -

C,, Alcohol 9 E 0 Daphnia magna - 10.07 -

‘5 Day Observation

10 APPENDIX 111


LC50 (” CHEMICAL SPECIES 24 HR 48 HR 96 HR. REE NO.

8

8

C,,Akohol 1EO (30%) Hermit Crab - 4,000* -

C , , ~ c o h o ~ 3E0 (30%) Hermit Crab - 3,500* -

(Isopropanol Soluiion)

Osomooanol Solution)

8

8

C16Alcoho19E0 (30%) Hermit Crab - 2,000* -

C1,,,Alcohol3EO (30%) Hermit Crab - 1*,500-4,000* -

(Isopropanol Soluiion)

Oxownan01 Solution)

8

8

22 22 22 22 22

C,,,,AlcoholbEO (30%) Hermit Crab - 4,000” -

C16.,,~cohol 9 E 0 (30%) Hermit Crab - 4,000* -

Qsopropanol Solution)

QsoprqamiSolunon) - C,,,, Alcohol 14EO Rainbow Trout 0.8 0.7

- - Brown Trout 1.0 0.7 GUPPY

Harlequin Fish 1.5 Minnow 3.4

- - - - - -

‘SDayObservatron

SULFATED ALCOHOLS AND ETHOXYLATES

LC, (mg/l) REF NO CHEMICAL SPECIES 24 HR 48HR. % 96HR.

56 DOBANOL 25-S Harlequin Fish - 10-100 -

DOBANOL 91-2.5s Rainbow Trout - 400-450** 400-450** 57 NEODOL 25-3A Bluegill Sunfish 32 32 32 58 NEODOL 25-35 Bluegill Sunfish 32 32 32 58

56 DOBANOL 25-33 Harlequin Fish - -10 -

NEODOL 25-3S40 (39%) DaDhnia 3.3 - 2.5 7 NEODOL 2 5 3 4 0 (39%) Bluegill Sunfish 9.5 - 7.3 7 DOBANOL 25-3N60 Rainbow Trout - 4.9* 6.3* 59

50 C,, AlcohoI 2 E 0 SO, Goldfish - 36.0 -

31 Daphnia 0.27( NOEC) - 1.17 31

- - 0.74(21day) 31

c14.16 2.25EO S0,Na Fathead Minnow O.lO(NOEC) __ -

‘3.1 and39 mgll regwtiidy for active matter. “130-147 mgllforacliLe mattey

11 APPENDIX 111

OTHER

LC, ( m g 4 CHEMICAL SPECIES 24 HR. 48 HR. 96 HR. REE NO.

56

- 49

Coconut Alcohol Harlequin Fish - 10-100 - Sodium Sulfate Oleic Alcohol 2 1 E 0 Goldfish 650(6 hr.) -

% ,

- 0.5-1.0 2 Flounder (eggs & larvae) - - 0.5-1.0 2

- 100 2 Clam - - 50 2 Mussel - - <5 2 Cockle -

Cr ustacean-decapods - >loo 2 - >loo 2 - 1.2 2

Tallow Alcohol lOEO Codfish (eggs & larvae) -

Leader adspersus - Leader squilla - Crustacean-(stage I1 - larvae) (Balanus balanoides) Hermit Crab - - >loo 2 Spider Crab (adult) - - >loo 2 (stage I larvae) - - 800 2

- > 100 2 51

0.8 0.7 51 51 0.7

0.4 0.4 51 2.6 2.3 51 2.7 2.5 51

56

Shore Crab -

Harlequin Fish _.L

Rainbow Trout - Rainbow Trout - Golden Orfe - Golden Orfe -

Tallow Alcohol 14E0 Goldfish 7.9(6 hr.) 2.1 -

. -

Coconut Alcohol 3 E 0 Harlequin Fish - 10-100 - Coconut Alcohol 7.5EO Bluegill Sunfish 12.3 12.3 12.3 45

12

APPENDIX IV

SPILL SITUATIONS Alcohol khoxylates that are spilled or leaked directly into a waterway pose a different problem from environmental run-offs or from the very dilute concentrations found in industrial or municipal effluents.

Material from spilled or broken drums of alcohol ethoxylates or leakage from storage tanks or rail cars may enter directly into a nearby stream or river. This puts a much greater stress on the environment than effluents containing alcohol ethoxylates. The concentration of spilled surfactant would probably be high, while effluent concentrations are very low, probably in the parts per million range. The spill is usually a local- ized condition and the initial concentration to which fish would be exposed may overwhelm their normal defense mechanisms and cause quick death.

ANALYSIS OF THE SITUATION When evaluating a spill situation, a number of factors must be taken into account before action can be taken or the potential risks evalu- ated. Unlike waterway spills, the LC,ds presented in this brochure were determined under laboratory situations with the specified concentration levels, water quality, species, and other variables already determined or controlled.

There are four basic factors that should be taken into account when assessing risks in a spill situation:

1. Determine which chemical was spilled. There is a large difference between the toxicities of the different surfactant products. Longer chain alcohols will not readily dissolve in water and may disperse forming a “blanket” over the surface. Alcohol ethoxylates dissolve readily, and ethoxysulfates may cause foaming.

2. Try to determine how much was spilled. Surfactants at 100% strength will be more toxic than a diluted solution. The initial concentration of material can affect the initial rate of biodegradation. Diluted solutions of alcohol ethoxylates will initially biodegrade much faster. Once biodegradation is initiated, the breakdown proceeds rapidly leav- ing less toxic residues which also biodegrade.

3. Take into account the quality of the receiving water. Temperature, pH, hardness, contaminants, turbidity, available nutrients, rate of flow, and salinity are just a few of the factors that may alter the predicted toxicity of chemicals to aquatic animals. For instance, as a general rule, chemicals are less toxic to aquatic animals in colder water because the animals’ respiration and metabolism rates are lower.

4. Get a rough idea of actual exposure of the spilled material to the aquatic animals. Are the large populations of fish upstream or downstream from the spill location?

Is the spill area population made up of healthy adults or is it composed of the more susceptible larvae or juveniles? Do the fish have a chance to swim from the contaminated area once they detect the spill? Is the spill in a fastmoving stream which will dilute the chemical or in a stag- nant pond or lake area?

ACTION IN SPILL SITUATIONS Removing the Source. If the spill is near the shore or is running into the waterway, attempt to dike off the flow quickly to allow as little as possible to contaminate the water.

If leaking or damaged drums cannot be removed quickly, dike the area around them to hold back any surfactant that may enter the waterway. If possible, position and brace the drums to minimize the amount that may spill.

Local authorities (Fish and Game Department o r a County Environmental Works Depart- ment) should be contacted and informed of the situation as quickly as possible. If the concentration in the water is high enough, a fish kill may result.

If the amount spilled into the waterway is large and/or involves multiple tanks cars, CHEMTREC (800-424-9300) or STEW (Shell Transportation Emergency Reporting Procedure) (713-473- 9461) should also be advised of the situation.

help to remove the broken drums from the area. Wear protective clothing to protect against skin and eye contact when working with the concentrated spilled material. Transfer the spilled material into EPA approved salvage drums or use a vacuum truck.

M e r diking the spill, obtain

For spills on land, do not flush surl‘actants away with water. This increases the possibility of having the material enter the waterway and may cause foaming which is harder to clean up. Scoop up the chemical and contaminated soil. Transfer the contaminated material into EPA approved salvage drums. The contaminated soil is removed from the area because subsequent rainfall may wash the residual material into the waterway.

If large spills enter or threaten to enter sewer drains that lead to municipal wastewater treatment plants, these facilities should be notified as soon as possible. Adjustments may have to be made to handle an increased chemical load on the waste treatment system. Con~ol of the Spill. Depending on the local situation, there are various options available for control of the spill once it has entered the water. I

possibIe, increase the water to the area of the spill; the

extra volume will dilute the surfactant and will increase the initial rate of biodegradation. Also, this dilution may reduce the surfactant concentration enough to prevent a fish kill. Other options, if the situation permits, are to divert the downstream flow, to dike or dam off the contaminated water.

Since the ambient bacterial or algal populations use Neodol surfactants as a carbon source, changing the environmental conditions to favor an increase in these populations may increase the ultimate rate of biodegradation. For example, aeration of small ponds or inlets will enhance algal growth.

existence at the time of the spill and beyond the human control will also influence the degree of toxicity and thus the overall effect of the spill on the aquatic life.

Other conditions already in

Some studies suggest that detergent products may be adsorbed onto organic material in the water, rendering much of the surfactant harmless to the fish population?5

The flow rate of a river or stream has a natural dilution effect on dissolved material and can bring the concentration below the toxic level. Rain also acts as a natural diluent.

The spilled Neodol alcohols pose a different problem from alcohol ethoxylates. The long chain alcohols are highly hydrophobic and unlike the alcohol ethoxylates which dissolve readily, these substances will float on the water. This stops oxygen from dif- hsing into the top layers of the water and will limit the respiration of animals living under the hydrophobic “cover”.

Such spills can be cleaned up by simple mechanical means (using booms to isolate the material and then scooping it up off the water surface) or by chemical interaction (the addition of a small amount of an emulsifier will disperse the material, increasing the surface area and thus the initial biodegradation rate). It must be emphasized, however, that chemical interaction is a much less desirable method of removal. This is because the emulsifier may cause the surfactant to go into the water column, possibly harming benthic (bottom-dwelling) organisms which are important to the food chain.

14

samplingikw Spill Area. To determine the concentration of the spilled material and its subsequent diffusion through still water or movement downstream, it is necessary to take samples for analysis.

locations that are representative of the spilled area. Therefore, it is better to take a few good samples than many poor ones. Samples give a “snapshot” picture of a continually changing situation. They must be collected in a proper manner and, unless properli stored, must be analyzed as soon as possible after being collected. Here is an example of sample locations in a spill situation. The spilled material enters a flowing river at some particular location. One sample is taken upstream to act as a control and two others are

Samples must be taken from

taken downstream to monitor the chemical’s movement.

The control sample will give the background concentration of any surfactant already present in the river. Analysis of the control will also give an estimation of “noise” or interference in the sample which can then be subtracted from the values obtained from downstream samples. The result is a base line from which elevated concentrations of a chemical can be calculated.

To preserve a sample for later analysis, any bacteria or algae in the sample must be killed as soon as possible after the sample has been taken. This will stop the biodegrading action of these microorganisms and keep the concentration of the unreacted surfactant at the level at which it was collected. In order to kill the microorganisms, 200 parts per million of mercuric chloride or a 1% solution of formalin (37% for- maldehyde, 63% water) should be added. Subsequent freezing should not alter the integrity of the sample.

Analysis for surfactant materials is by the Cobalt Thiocyantate Active Substance (CTAS60) or Methylene Blue Active Substance (MBAP) methods. Details on these methods and correct proce- dures for analysis can be obtained from Shell Development Com- pany at our Westhollow Research Center in Houston.

SAFETY INFORMATION FOR NEODOL@ PRODUCTS Neodol ethoxysulfates are COM- BUSTIBLE. They must be kept away from any source of ignition such as heat, sparks and open flame. Neodol alcohols and ethoxylates can also catch fire, but generally only in contact with flames.

Neodol products should be stored in tightly closed containers, in a clean, well-ventilated area away from heat and open flame. Do not smoke where these products are stored. handled or used.

Use water fog to fight large fires. Fire extinguishers for small or confined fires should be of the CO, or dry chemical types. Wear self-contained breathing apparatus when fighting fires in confined areas.

Neodol products can cause eye irritation. Wear splash-proof safety glasses or a face shield if there is danger of these products splashing into your eyes. Should eye contact occur, eyes should be immediately flushed with large amounts of water for at least 15 minutes. If irritation persists, seek medical attention.

Use Neodol products in a well-ventilated area. High vapor concentration or prolonged exposure can cause headache, dizzi- ness, nausea and vomiting.

If this happens, remove the victim to fresh air and get medical attention ;?s soon as possible. Give artificial respiration if breathing has stopped. Keep the victim warm but not hot.

Short-term skin contact with Neodol is relatively harmless. Fre- quent contact can be mildly irritat- ing to the skin.

Use good working habits and proper hygiene. Wear rubber gloves and other protective clothing. If Neodol products soak your *

clothes, undress and take a shower. Launder the contaminated clothes before putting them on.

Do not eat or smoke in areas where Neodol alcohols are handled, processed or stored. Hands and other exposed parts of the. body should be washed with soap and water before eating, smoking or using toilet facilities.

15

SHIPPING DATMSTORAGE AND HAAiDLING

Inedible fatty alcohol

compound Box car Combustible

Tank truck NA 1993 Combustible liquid N.O.SAd) Liquid‘n

25-3A 8.50 0.0032 0.0054 8 40 44W) Detergents Combustible liquid N.O.S.’d)

NA 1993 0.0034 0.0054 8 Tankcar 40 440‘c’ 25-3s 8.76 Liquid washing compound Placarded-combustible

(a) Shell does not ofler less-than bulk quantities direct, a c q t assanples. Drum shipments are available through authorized divrihton. e) Umjhmfieigbt chi&ation (UFC) and consolidated@dght clarsifkation (CFC) ful& remoLlable open head drum, Rule 40 (2OfI8gauge). (c) Po!velbylenc lined drum, steel ow?pack (DOT 2SL and37M. 24/22 gauge). (d) Under inedptwn is the DOTHarmdous Material Name. (e) DOT-Federal Department of Ranqwrtatibn. 03 Drum &@menis are not regulated ly the DOZ

STORAGE AND HANDLING Complete details on the storage andbandling of NEODOL alcohols, ethqlates andethoxysuvates are contained in an illuurated bookler (SC:133) awilable upon request

c

16

Gerwral Bibliography

17

Further safety information on the entire Neodol product line is available in tlie Shell 8-p;igge lxo- chure entitled Safety Infoi-mation for NEOL>OL@ Products, SC: 241.

WARRANTY A1 products purchased from Shell are subiect t o terms and concli- tions set out in the contract, order acknowledgnient and/or bill o f lading. Shell ~ a r r m t s only that its product will meet those specifica- tions designated ;IS such herein or in other Shell publications. All other information supplied by Shell is considered accurate I ~ u r is furnished upon the express condition that the customer shall nuke its own assessment to determine the product’s suitability for a particular’purpose. No warranty b expressed or implied regarding such other information, the data upon which the same 13 based, or the results to be obtainedfiom the use thereoj that any product shall be merchantable orfit for any particularpurpose; or that the use of sucf2 other information orproduct will not infringe any patent.

IVEOL~OI~~ I’KCIIN ‘c7:Y

(404) 95 5-4600 320 Interstiire North I%~rku-a!. Atlanta, Georgia 30339

Chicago (312) 887-5500 1415 West 22nd Street Oak Brook, Illinois 60521

Cleveland ( 2 1 6 ) 842-4000 7123 Pearl Road Cleveland, Ohio 44130

Houston (713) 526-4631 2001 Kirby Drive Houston, Texas 77019

Los Angeles

51 1 N, I3rookhursr Street iinaheim , C:r 1 i fc mi i:i 92803

West Orange (201 325-5200 100 Executive 1)rive West Orange. NewrJcrsej.07051!

At la I1 td

(714) 991-9200

FOR I“if EI4kATIO.U l. Srl LE3 CONlACl

kcten Chemicals, Inc. (713) 241-6161 One Shell Plaza Houston, Texas 77002

Documents

The Aquatic Safety of Neodol Products - InfoHouseinfohouse.p2ric.org/ref/27/26508.pdf · 2 INTIiODlJCTION NEODOL @products, composed of alcohols, alcobol eth0.aylate.s and alcohol