Experimental Studies of Molybdenum Physiology and Toxicity

Molybdenum toxicity studies with fish

International Molybdenum Association
Toxicity Testing Programme: Aquatic organisms

Substance

Toxicity/ mg/l


acute fish a

acute daphnids b

algal growth c


96 h LC50

48 h EC50

72 h IC50

Molybdenum trioxide (pure)

130

150

100

Molybdenum trioxide (tech)d

77

88

100

Ammonium dimolybdatee

420

140

41

Sodium molybdate

7600

330

>100

Risk phrase required if:

<100

<100

< 100

Notes

a Acute fish toxicity is representive of relative toxicity to aquatic vertebrates. Trout used because of large data base and sensitivity. Rainbow trout (10/concentration) exposed to various concentrations under semi-static conditions for 96 hours.

b Acute daphnia toxicity is representative of relative toxicity to aquatic invertebrates. Dapnids are ubiquitous thoughout the world in fresh water ponds and lakes, important link in food chain. Daphnids (20/concentation) exposed to various concentrations under static conditions for 48 hours. Daphnids observed for immobilization and Effective Concentration, EC50 calculated.

c Algal growth inhibition is representative of relative toxicity to aquatic plants. Algae are primary producers in the food chain. Inhibition can alter food web and reduce productivity of ecosystems. Stimulation may cause algal blooms, causing anoxic conditions, negative anaesthetic effects, etc. Test cultures of algae were prepared and added to solutions of test material and incubated for 72 hours. Growth was monitored by measuring the absorbance of each culture at 665 nm. The median effective concentration for inhibition of growth (IC50 ) after 72 hours was calculated.

d The aquatic toxicity of technical oxide varied with the level of impurities, particularly copper. High copper content samples gave lower results in the daphnia studies.

e The toxicity of ammonium molybdate to algae is not unexpected considering the the known toxicity of ammonia, which is commonly used as a bactericide and disinfectant.

Acute toxicities of molybdenum compounds towards fish

LD50/mg/l

Compound

Species

24h

48h

96h

No effect Level

MoO3 [1]

bluegill

87-120

87-120

87

75


rainbow trout

102

65-87

65-87

65

Ammonium dimolybdate[2]

bluegill

166

157

157

140


rainbow trout

138

135

120

87

Sodium molybdate [2]

bluegill

> 10,000

-

6,790

2,400


rainbow trout

> 10,000

-

7,340

3,200


channel catfish

> 10,000

-

> 10,000

7,500


fathead minnow

> 10,000

-

7,630

5,600

Sodium molybdate [3]

shrimp

3997

-

-

-


minnow

6590

-

-

-


American oyster (EC50)

3526

-

-

-

[1] Bentley, R. E., Acute Toxicity of Ammonium Molybdate and Molybdic Trioxide to Bluegill (Lepomis macrochirus) and Rainbow Trout (Salmo gairdneri),Bionomics, Wareham, Massachusetts, 1975, January
[2] Bentley, R. E., Acute Toxicity of Sodium Molybdate to Bluegill (Lepomis macrochirus), Rainbow Trout (Salmo gairdneri), Fathead Minnow (Pimephales promeals), Channel Catfish (Ictalurus punctatus), Water Flea (Daphnia magna) and Scud (Gammarus fasciatus),Bionomics, Wareham, Massachusetts, 1973, December.
[3] Knothe, D. W. and van Riper, G. G., Bull. Environ. Contam. and Toxicol., 1988, 40, 785.

Sodium molybdate was found to be significantly less toxic to several varieties of fish than either molybdic oxide or ammonium dimolybdate [ Bentley, 1973; 1975].

Bentley, R. E., Acute Toxicity of Sodium Molybdate to Bluegill (Lepomis macrochirus), Rainbow Trout (Salmo gairdneri), Fathead Minnow (Pimephales promeals), Channel Catfish (Ictalurus punctatus), Water Flea (Daphnia magna) and Scud (Gammarus fasciatus), Bionomics, Wareham, Massachusetts, 1973.
Bentley, R. E., Acute Toxicity of Ammonium Molybdate and Molybdic Trioxide to Bluegill (Lepomis macrochirus) and Rainbow Trout (Salmo gairdneri), Bionomics, Wareham, Massachusetts, 1975.

Toxicity rainbow trout

The purpose of the study was to resolve inconsistencies in reported bioassays of the toxicity of molybdenum (as sodium molybdate in water) to fertilized rainbow trout eggs and alevins (EA) for which a wide toxicity range (LC50 0.73 to >90 mg/L Mo) has been reported. Molybdenum was not acutely toxic to the early life stages of rainbow trout (32 d, maximum molybdenum concentration 400 mg l-1). When early life stages of rainbow trout were exposed to a maximum molybdenum concentration of 1500 mg l-1 for 32 d there was not sufficient mortality for an LC50 to be calculated. The importance of careful control of the water chemistry in the bioassay was emphasized.

Davies, T. D., Pickard, J., and Hall, K. J., Acute molybdenum toxicity to rainbow trout and other fish, Journal of Environmental Engineering and Science, 2005, 4, 481-485.

Aquatic Organisms

The benthic [sediment] organisms Chironomus plumosus larvae and Tubifex tubifex worms may be used as aquatic toxicity indicators of metals which may accumulate in freshwater sediments as a consequence of heavy metal contamination of water. The LC50 values after 96 h are given in the Table. The tests were carried out in boiled tap water (20 C, pH 7 - 8, calcium carbonate hardness 80 mg l-1). Molybdate (supplied as ammonium hepatamolybdate) is the least toxic of the metals on both a mass and molar basis and is non-toxic, its LC50 value being less than concentrations found in the environment.

Toxicities of metals towards aquatic organisms

 

C. plumosus

T. tubifex

Compound

103LC50/mg l-1

103LC50/ mol l-1

103LC50/mg l-1

103LC50/ mol l-1

V2O5

218

4.28

211

4.14

(NH4)6Mo7O24.4H2O

455

4.74

4563

47.6

MnSO4.H2O

68

1.24

295

5.37

NiSO4.7H2O

266

4.53

537

9.15

CuSO4.5H2O

0.105

0.00165

2

0.0315

Cu2Cl2

0.927

0.0146

6

0.0945

Fargasova, A, Comparative acute toxicity of Cu2+, Cu+, Mn2+, Mo6+, Ni2+ and V5+ to Chironomus plumosus larvae and Tubifex tubifex worms, Biologia, 1998, 53, 315-319.

Mo toxicity towards flannelmouth sucker

Larval flannelmouth sucker (Catostomus latipinnis) were exposed to inorganics which simulated environmental ratios reported for sites along the San Juan River. The toxicity rank order was copper > zinc >vanadium > selenite > selenate > arsenate > uranium > boron > molybdenum.

Hamilton, S.J., Buhl, K.J., Hazard evaluation of inorganics, singly and in mixtures, to flannelmouth sucker Catostomus latipinnis in the San Juan River, New Mexico, Ecotoxicology And Environmental Safety, 1997, 38, 296-308.

Toxicity towards Daphnia

Molybdates are alternatives to toxic chromates in industrial applications, e.g. passivation of zinc coatings in the automobile industry. Molybdates are much less toxic than chromates although both molybdenum and chromium and their compounds are included in th List II of European dangerous substances directive (Council of the European Communities (1976). Directive of 4 May 1976 on Pollution Caused by Certain Dangerous Substances and Discharged into the Aquatic Environment of the Community (76/464/EEC, OJL 129, 18 May). The purpose of the work described in this paper was to compare the aquatic acute and chronic toxicity of Mo and Cr in standard tests with the organism Daphnia magna, and in acetylcholinesterase inhibition.

Acute toxicity towards Daphnia magna in ASTM hard water

Chemical

48 h LC50/mg L-1

95% confidence limit

Sodium dichromate

0.29

0.269-0.315

Sodium molybdate

2848

2839-2857


Chronic toxicity towards Daphnia magna in ASTM hard water

Chemical

Total growth

Reproduction

Mortality


NOEC
/mg L-1

LOEC
/mg L-1

EC50
/mg L-1

NOEC
/mg L-1

LOEC
/mg L-1

EC50
/mg L-1

NOEC
/mg L-1

LOEC
/mg L-1

EC50
/mg L-1

Sodium dichromate

0.0125

0.025

0.233

0.0125

0.025

0.047

0.075

0.01

0.524

Sodium molybdate

50

75

204

50

75

102

75

100

255


Daphnia magna acetylcholinesterase inhibition in vivoa

Chemical

NOEC/mg L-1

LOEC/mg L-1

EC50 /mg L-1

Sodium dichromate

0.075

0.15

0.632

Sodium molybdate

750

1500

26.5

a No inhibition in vitro

The study shows that sodium molybdate is much less toxic towards Daphnia magna than is sodium dichromate.

Diamantino, T.C., Guilhermino, L., Almeida, E., and Soares, A. M. V. M., Toxicity of sodium molybdate and sodium dichromate to Daphnia magna Straus evaluated in acute, chronic, and acetylcholinesterase inhibition tests, Ecotoxicology and Environmental Safety, 2000, 45, 253-259.