Lyndsey Overlin

TOXICOLOGY OF NICKEL

Basic Chemical Properties of Nickel

This metal doesn’t oxidize very quickly

There are a few common oxidation states+2 Ni, +1 Ni, and

+3 NiThe most common:

+2 Ni

Basic Physical Properties of Nickel

It conducts heat and electricity fairly well

It’s magneticThere are 14 known

isotopes, 5 naturally occurring of NickelNi 58 (68.27%) Ni 60 (26.10%)Ni 61 (1.1%)Ni 62(3.6%)Ni 64 (0.9%)

Chemical Properties (cont.)There are also 6

major radioactive isotopes of which Ni 59 and Ni 63 have the most prevalent half-lifeNi 59: 75 000 years

(captures electrons)

Ni 63: 96 years (emits beta particle)

Origin and History of Nickel UseNickel was used as an alloying metal almost 2000 years

before is it officially discovered200 B.C.E the Chinese used Copper ore for manufacturingIt was from this copper ore that Nickel was eventually

isolatedDiscovered in 1751 by Axel Fredrik CronstedtBy 1844 the demand for Nickel had significantly increased It is thought that Nickel came from an ancient meteor

impact creating Ore Estimated Crustal Abundance: 8.4×101 milligrams per

kilogram Estimated Oceanic Abundance: 5.6×10-4 milligrams per liter

Uses and ApplicationsNickel is

manufactured for use in products such as:AlloysSteel

ManufacturingElectroplatingBatteriesElectronicsOther chemical

uses

How does it get into the Aquatic Environment?

Sediment Insoluble forms with silicates and sulfides as well

as soluble forms (run-off)Atmosphere

Mainly from the burning of fossil fuels which emits oxides, sulfides, silicates, as well as many soluble forms (particulates in rain water)

WaterLeaching from rocks

Once Nickel is in the Aquatic Environment…

Deep water concentrations range from 0.1 to 0.5 ppb Ni, whereas surface water contains 15–20 ppb

Divalent Nickel is the most common form within this environment

How Ni toxicity and water chemistry interact is not well understood.

Enhances microbial growth at LOW concentrations

It typically occurs as soluble salts absorbed in sediments, organic matter, or by biota

Van Baalen and O’Donnell, 1978

Toxicity to Aquatic Life?Some suggest it is

essential in some concentrations

Higher concentrations result in variable effects on marine lifeLife expectancy is

significantly altered for Daphnia at 40 ppb

LD50 for marine lobsters is between 150-300 ppm

Variable in fish species

Toxic EffectsHumans:

Lung and nasal cancers when inhaledNickel dermatitisCarcinogenic

Animals:Lung tumorsImpaired immune systemsDecreased number of live pups, increased pup mortalitySperm abnormalities

STUDIES OF EFFECTS ON AQUATIC BIOTA ARE LIMITED TO PHYTOPLANKTON AND CYANOBACTERIA!!

Mode of Entry The majority of cyanobacteria and phytoplankton studied within the

aquatic environments require Nickel for: Urease ((NH2)2CO +2H20 →H2CO3 + 2NH3) Hydrogenase ((2H+ 2e- H+ + H- H2)

However, comparison of BCF’s (bioconcentration factor) and BSAF’s (biosediment accumulation factors) in various aquatic organisms shows a different story

Also, the higher the solubility of Nickel, the higher the nickel uptake of various organisms Based on this it is more likely that Nickel is taken up through pore water

within sediments instead of ingestion Nickel that is onsiluble enter cells through phagocytosis and enter

into the cell in vacuoles. These vacuoles are acidified which causes the nickel to become soluble.

Once in the nucleus, heterochromatin areas in the long arm of the X chromosome is damaged as Ni 2+ replaces Mg 2+.

Molecular Mode of Toxic Interaction

It has been shown that a low levels, Nickel is actually a requirement for many organisms

However, once a threshold is reached, Ni can cause variable damage in organismsIn plants: Increase levels of Nickel can result in

decreasing chlorophyll contents and leaf photosynthetic activities through impairing permeability of membranes to other essential elements such as Iron.

In other organisms: Suppression of the uptake of Zn, Cu, Fe, Mn, Ca, Mg, and S

As these are suppressed by Nickel, parts of DNA can be silenced (not mutated) leading to cancer

Biochemical Metabolism and Breakdown

In order to better understand these processes, much research has been done on tissue accumulation of Nickel on various organismsCrayfish tend to have higher concentrations in the

gills and the digestive gut when exposed to high levels of Nickel. It was discovered that they go through a 2 week active uptake process and then a 2 week active excretion process (which isn’t correlated with the organs)

When looking at Catfish, concentrations of Nickel were as follows: kidney>liver>gill>intestine. From this it was inferred that fish are actively breaking down nickel through chloride cells in the kidney

Sediments

5X Ni RhInternal Standard

Correction Concentration Blank Correction Ratio Dilution

blank 2333 530789 2686 0.71651374180

1A 28592 547591 31901 9.38024335397 8.66372961217 0.47555 4.554587

1B 37262 516052 44115 13.00222645608 12.28571271428 0.554367 5.540421

1C 34858 531160 40096 11.81025521444 11.09374147264 0.430928 6.435965

2 34739 590330 35953 10.58184573468 9.86533199288 0.513765 4.800512

3 16901 548859 18813 5.49899272880 4.78247898700 0.443503 2.695854

4 47760 542499 53788 15.87066663990 15.15415289810 0.341452 11.09537

5 86965 510420 104097 30.78916366557 30.07264992377 0.40096 18.75042

6 43011 524010 50149 14.79129708028 14.07478333848 0.50839 6.921253

7 40653 545112 45565 13.43208193486 12.71556819306 0.467183 6.804379

8 37027 551353 41031 12.08755090761 11.37103716581 0.604947 4.699189

CRM 5x Ni

396677.4 516807.6 468952 138.98426199890

Tissues

10X Ni RhInternal Standard Curve

Correction Concentration Blank Correction Ratio Dilution

1 49936 562479 54241.1833 16.00494434 0.069482 115.1736

2 1552 585311 1620.175367 0.400588745

4 2525 597484 2581.601117 0.685692165 0.053638 6.391807

5 4707 587049 4899.166822 1.372948467 0.052547 13.06404

6 2024 586822 2107.52309 0.545107968 0.051819 5.259712

7 9701 582876 10168.19655 2.93543875 0.057541 25.50721

7 3030 566838 3266.306739 0.888736356 0.06097 7.288281

8 4178 587588 4344.284408 1.208402351 0.062778 9.62435

Colorado Lagoon

1. Our values we obtained for Nickel in the Colorado Lagoon were nowhere near the thresholds that have been set forth by the EPA2. Hydrology and Water Quality reports on the Lagoon

do not define Nickel to be one of the primary metals for concern

ERL ERM BPTCP CL-West CL-East CL-1 CL-2 Cl-3Nickel 21 51.6 34 36 32

18 14 8.9mg/kg (dry)

Concentrations that are underlined indicate ERM exceedences

ReferencesArgonne National Laboratory. (2005). “Nickel: Human Health Fact Sheet”.

Environmental Science Division. 1-2Alikhan, M.A., Bagatto, G., and Zia, S. 1990. The crayfish as a “biological indicator” of aquatic contamination by heavy metals. Water Res. 24: 1069–1076.Azeez, P.A., and Banerjee, D.K. 1991. Nickel uptake and toxicity in cyanobacteria. Toxicol. Environmental Chemistry 30: 43–50.Costa, Max; Davidson, Todd L.; Chen, Haobin; Ke, Quingdong; Zhang, Ping; Yan, Yan; Huang, Chuanshu; and Kluz, Thomas. (2005). “Nickel carcinogenesis: Epigenetics and hypoxia signaling”. Mutation Research/Fundamental and Molecular Mechanisms of Mutagenesis. 592(1-2) 79-88.Denkhaus, E. and Salnikow, K. (2002). “Nickel essentiality, toxicity, and carcinogenicity”. Critical Reviews in Oncology/Hematology. V42:35-56Eco-SSL. (2007). “Ecological Soil Screening Levels for Nickel”. U.S. Environmental Protection Agency. OSWER Directive 92857.7-76. 1-133.Eskew, D.L., Welch, R.M., and Cary, E.E. 1983. Nickel, an essential element for legumes and possibly all higher plants. Science (Washington), 222: 621–623.Gikas, Petros. (2008). “Single and combined effects of nickel (Ni(II)) and cobalt (Co(II)) on activated sludge and on other aerobic microorganisms”. Journal of Hazardous Materials. 159:187-203.

References (continued)Kozlova, Tatianna; Wood, Chris M.; and McGeer, James C. (2009). “The effect of water

chemistry on the acute toxicity of nickel to the cladoceran Daphnia pulex and the development of a biotic ligand model”. Aquatic Toxicology. 91:221-228.

Munzinger, Armin. (1990). “Effect of nickel on daphnia magna during chronic exposure and alterations in the toxicity to generations pre-exposed to nickel”. Water Research. 24: 845-852.

Muyssen, B.T.A; Brix, K.V.; DeForest, D.K.; and Janssen, C.R. (2004). “Nickel essentiality and homeostasis in aquatic organisms”. Environmental Reviews. 12:113-131.

Oller, Adriana R. (2002). “Respiratory Carcinogenicity Assessment of Soluble Nickel Compounds”. Environmental Heal Perspectives Supplements. 110 (5).

U.S. Environmental Protection Agency. (1999). Integrated Risk Information System (IRIS) on Nickel, Soluble Salts. National Center for Environmental Assessment, Office of Research and Development, Washington, DC.

Van Baalen, C. and O’Donnell, R. (1978). “Isolation of a nickel dependent blue-green alga”. Journal of General Microbiology. 105:351-353

Yang, X.; Baligar, V.C.; Martens, D.C., and Clark, R.B. (1996). “Plant Tolerance to Nickel Toxicity: II Nickel Effect on Influx and Transport of Mineral Nutrients in Four Plant Species”. Journal of Plant Nutrition. 19:265-279.