Environmental impact of silver

nanoparticles
In 2015, 251 million tubes of toothpaste were sold in the United States.[1] A single tube holds
roughly 170 grams of toothpaste, so approximately 43 kilotonnes of toothpaste get washed
into the water systems annually.[2] Toothpaste contains silver nanoparticles, also known as
nanosilver or AgNPs, among other compounds.[2]

Each tube of toothpaste contains approximately 91  mg of silver nanoparticles, with

approximately 3.9 tonnes of silver nanoparticles entering the environment annually.[3] Silver
nanoparticles are not entirely cleared from the water during the wastewater treatment
process, possibly leading to detrimental environmental effects.[2]

Contents
Silver nanoparticles in toothpaste
Wastewater treatment
Transformation in the environment
Chemical reactions in seawater
Effect on bacteria
Toxicology in aquatic environments
See also
References

Silver nanoparticles in toothpaste

Silver nanoparticles are used for catalyzing chemical reactions, Raman imaging, and
antimicrobial sterilization.[4] Along with its antimicrobial properties, its low mammalian cell
toxicity makes these particles a common addition to consumer products.[4] Washing textiles
embedded with silver nanoparticles results in the oxidation and transformation of metallic Ag
into AgCl.[5]

Silver nanoparticles have different physicochemical characteristics from the free silver ion,
Ag+ and possess increased optical, electromagnetic, and catalytic properties.[4] Particles with
one dimension of 100 nm or less can generate reactive oxygen species. Smaller particles less
than 10  nm may pass through cellular membranes and accumulate within the cell.[4] Silver
nanoparticles were also found to attach to cellular membranes, eventually dissipating the
proton motive force, leading to cell death.[4]

Silver nanoparticles that are larger than the openings of membrane channel proteins can
easily clog channels, leading to the disruption of membrane permeability and transport.[4]
However, the antimicrobial effectiveness of silver nanoparticles has been shown to decrease
when dissolved in liquid media.[4]

The free silver ion are potentially toxic to bacteria and planktonic species in the water.[4] The
positively charged silver ion can also attach to the negatively charged cell walls of bacteria,
leading to deactivation of cellular enzymes, disruption of membrane permeability, and
[4]
eventually, cell lysis and death.[4] However, its toxicity to microorganisms is not overtly
observed since the free silver ion is found in low concentrations in wastewater treatment
systems and the natural environment due to its complexation with ligands such as chloride,
sulfide, and thiosulfate.[4]

Wastewater treatment

A majority of silver nanoparticles in

consumer products go down the
drain and are eventually released
into sewer systems and reach
wastewater treatment plants.[5]
Primary screening and grit removal
in wastewater treatment does not
completely filter out silver
nanoparticles, and coagulation
treatment may lead to further
condensation into wastewater
sludge.[2] The secondary wastewater
treatment process involves
suspended growth systems which
allow bacteria to decompose organic
matter within the water.[2] Any silver
nanoparticles still suspended in the
water may collect on these microbes, Some occurrences of interactions of AgNPs in wastewater
potentially killing them due to their treatment systems are depicted.
[2]
antimicrobial effects. After passing
through both treatment processes,
the silver nanoparticles are eventually deposited into the environment.[2]

A majority of the submerged portions of wastewater treatment plants are anoxic and rich in
sulfur.[6] During the wastewater treatment process, silver nanoparticles either remain the
same, are converted into free silver ions, complex with ligands, or agglomerate.[7] Silver
nanoparticles can also attach to wastewater biosolids found in both the sludge and the
effluent.[7] Silver ions in wastewater are removed efficiently because of their strong
complexation with chloride or sulfide.[8]

A majority of the silver found in wastewater treatment plant effluent is associated with
reduced sulfur as organic thiol groups and inorganic sulfides.[8] Silver nanoparticles also tend
to accumulate in activated sludge, and the dominant form of the silver found in sewage sludge
is Ag2S.[8] Therefore, most of the silver found in wastewater treatment plants is in the form of
silver nanoparticles or silver precipitates such as Ag2S and AgCl.[7]

The amount of silver precipitate formed depends on silver ion release, which increases with
increasing dissolved oxygen concentration and decreasing pH.[9] Silver ions account for
approximately 1% of total silver after silver nanoparticles are suspended in aerated water.[9]
In anoxic wastewater treatment environments, silver ion release is therefore often negligible,
and most of the silver nanoparticles in wastewater remain in the original silver nanoparticle
form.[9] The presence of natural organic matter can also decrease oxidative dissolution rates
and therefore the release rate of free silver ions.[9] The slow oxidation of silver nanoparticles
may enable new pathways for its transfer into the environment.[9]

Transformation in the environment

The silver nanoparticles that pass through wastewater treatment plants undergo
transformations in the environment through changes in aggregation state, oxidation state,
precipitation of secondary phases, or sorption of organic species.[10] These transformations
can result in the formation of colloidal solutions. Each of these new species potentially have
toxic effects which have yet to be fully examined.[10]

Most silver nanoparticles in products have an organic shell structure around a core of Ag0.[10]
This shell is often created with carboxylic acids functional groups, usually using citrate,
leading to stabilization through adsorption or covalent attachment of organic compounds.[10]
In seawater, glutathione reacts with citrate[10] to form a thioester via esterification.[11]

Thioesters exhibit electrosteric repulsive forces due to amine

functional groups and their size, which prevents
aggregation. These electrostatic repulsive forces are
weakened by counterions in solution, such as Ca2+ found in
seawater. Ca2+ ions are naturally found in seawater due to
the weathering of calcareous rocks, and allow for dissolution Esterification reaction of citrate and
of the oxide-coated particle at low electrolyte glutathione
concentrations.[6]

This leads to the aggregation of silver nanoparticles onto thioesters in seawater.[6] When
aggregation occurs, the silver nanoparticles lose microbial toxicity, but have greater exposure
in the environment for larger organisms.[6] These effects have not been completely identified,
but may be hazardous to an organism’s health via biological magnification.[6]

Chemical reactions in seawater

Solubility Products (Ksp) of Silver-Containing Solids[12]

Ag2O 4.00 x 10−11

Ag2CO3 8.46 x 10−12

AgCl 1.77 x 10−10

Ag2S 5.92 x 10−51
Ag2SO4 1.20 x 10−5

Silver nanoparticles are thermodynamically unstable in oxic environments.[5] In seawater,

silver oxide is not thermodynamically favored when chloride and sulfur are present. On the
surface where O2 is present in much greater quantities than chloride or sulfur, silver reacts to
form a silver oxide surface layer.[13] This oxidation has been shown to occur in nanoparticles
as well, despite their shell.[13]

Dissolution of Ag2O in Water:

Ag2O + H2O → 2Ag− + 2OH− [11][13]

The nano-size of the particles aids in oxidation since their smaller surface area increases their
redox potential.[14] The silver oxide layer easily dissolves in water because of its low Ksp value
of 4×10−11.[14]
 Possible Oxidation Reactions of Silver:

Ag + O2 → Ag+ + O2−

4Ag + O2 → 4Ag+ + 2O2−[15]

In aerobic, acidic seawater, oxidation of Ag can occur through the following reaction:

Oxidation of Silver in Seawater:

2Ag(s) + ½ O2(aq) + 2H+(aq) ⇌ 2Ag+(aq) + H2O(l) [15]

The formation of these Ag+ ions are a concern for environmental health, as these ions freely
interact with other organic compounds, such as humic acids, and disrupt the normal balance
of an ecosystem.[15] These Ag+ ions will also react with Cl− to form complexes such as AgCl2−,
AgCl32−, and AgCl43−, which are bioavailable forms of silver that are potentially more toxic to
bacteria and fish than silver nanoparticles.[15] The etched structure of silver nanoparticles
provides the chloride with the preferred atomic steps for nucleation to occur.[16]

Reaction of Silver with Chloride:

Ag+ + Cl− → AgCl

AgCl(s) + Cl−(aq) → AgCl2−(aq) [16]

Ag has also been shown to readily react with sulfur in water.[17] Free Ag+ ions will react with
H2S in the water to form the precipitate Ag2S.[17]

Silver and Sulfur Reaction in Seawater:

2Ag(aq) + H2S(aq) → Ag2S(s) + H2(aq) [18]

H2S is not the only source of sulfur that Ag will readily bind to. Organosulfur compounds,
which are produced by aquatic organisms, form extremely stable sulfide complexes with
silver.[18] Silver outcompetes other metals for the available sulfide, leading to an overall
decrease in bioavailable sulfur in the community.[18] Thus, the formation of Ag2S limits the
amount of bioavailable sulfur and contributes to a reduction in toxicity of silver nanoparticles
to nitrifying bacteria.[13]
Effect on bacteria

Silver nanoparticles are experimentally shown to inhibit autotrophic nitrifying bacterial

growth (86±3%) more than Ag+ ions (42±7%) or AgCl colloids (46±4%).[4] Silver nanoparticle-
inhibited heterotrophic growth (55±8%) in Escherichia coli is best observed at lower
concentrations, between 1.0 uM and 4.2 uM.[4] This is less than Ag+ ions (~100%), but greater
than AgCl colloids (66±6%).[4] The actual cause of these results is undetermined as growth
conditions and cell properties differ between nitrifying bacteria and heterotrophic E. coli.[4]
Studies conducted in natural lake environments show less response from bacterioplankton
than in laboratory environments when exposed to similar concentrations of silver
nanoparticles. This may be due to the binding of free Ag+ ions to dissolved organic matter in
lake environments, rendering the Ag+ unavailable.[19]

Within toothpaste, Ag+ ions have been shown to have a stronger effect on gram-negative
bacteria than on gram-positive bacteria.[3] In comparison to other nanoparticles, such as gold,
silver tends to have a broader antimicrobial effect, which is another reason why it is
incorporated into so many products.[3] Ag+ is less effective on gram-positive bacteria due to
the thick layer of peptidoglycan around them that gram-negative species lack.[3]
Approximately half of the peptidoglycan wall is composed of teichoic acids linked by
phosphodiester bonds, which results in an overall negative charge in the peptidoglycan
layer.[20] This negative charge may trap the positive Ag+ and prevent them from entering the
cell and disrupting the flow of electrons.[20]

Toxicology in aquatic environments

The most environmentally relevant species of these nanoparticles are silver chloride within
marine ecosystems and organic thiols within terrestrial ecosystems. Once Ag0 enters the
environment, it is oxidized to Ag+.[21] Of the potential species formed in seawater, such as
Ag2S and Ag2CO3, AgCl is the most thermodynamically favored due to its stability, solubility,
and the abundance of Cl− in seawater.[21] Research has shown that partially oxidized
nanoparticles may be more toxic than those that are freshly prepared.[4]

It was also found that Ag dissolutes more in solution when the pH is low and bleaching has
occurred.[21] This effect, coupled with ocean acidification and increasing coral reef bleaching
events, leads to a compounding effect of Ag accumulation in the global marine ecosystem.[21]
These free formed Ag+ ions can accumulate and block the regulation of Na+ and Cl− ion
exchange within the gills of fish, leading to blood acidosis which is fatal if left unchecked.
Additionally, fish can accumulate Ag through their diet. Phytoplankton, which form the base
level of aquatic food chains, can absorb and collect silver from their surroundings.[22]

As fish eat phytoplankton, the silver accumulates within their circulatory system, which has
been shown to negatively impact embryonic fish, causing spinal cord deformities and cardiac
arrhythmia.[22] The other class of organisms heavily affected by silver nanoparticles is
bivalves.[22] Filter feeding bivalves accumulate nanoparticles to concentrations 10,000 times
greater than was added to seawater, and Ag+ ions are proven to be extremely toxic to them.[22]

The base of complex food webs consists of microbes, and these organisms are most heavily
impacted by nanoparticles.[22] These effects cascade into the problems that have now reached
an observable scale.[23] As global temperatures rise and oceanic pH drops, some species, such
as oysters, will be even more susceptible to the negative impacts of nanoparticles as they are
stressed.[23]

See also
 Environmental impact of pharmaceuticals and personal care products
Plastic resin pellet pollution

References
1. FoodIndustryMagazine. (n.d.). Toothpaste unit sales in U.S. supermarkets in 2014 and 2015.
2. Brar S, Verma M, Tyagi R, Surampalli R (2009). Engineered Nanoparticles in Wastewater and
Wastewater Sludge - Evidence and Impacts. Waste Management, 30: 504-520.
3. Junevičius J, Žilinskas J, Česaitis K, Česaitienė G, Gleiznys D, Maželienė D (2015). Antimicrobial
activity of silver and gold in toothpastes: A comparative analysis. Stomatologija, Baltic Dental and
Maxillofacial Journal, 17 (1): 9-12.
4. Choi, O., Deng, K. K., Kim, N. J., Ross, L., Jr., Surampalli, R. Y., & Hu, Z. (2008). The inhibitory effects
of silver nanoparticles, silver ions, and silver chloride colloids on microbial growth. Water Res,
42(12), 3066-3074.
5. Kaegi, R., Voegelin, A., Sinnet, B., Zuleeg, S., Hagendorfer, H., Burkhardt, M., & Siegrist, H. (2011).
Behavior of metallic silver nanoparticles in a pilot wastewater treatment plant. Environmental
Science Technology, 45(9), 3902-3908. doi:10.1021/es1041892.
. Li X, Lenhart J, Walker H (2010). Dissolution-Accompanied Aggregation Kinetics of Silver
Nanoparticles. Langmuir, 26 (22): 16690-16698.
7. Hou, L., Li, K., Ding, Y., Li, Y., Chen, J., Wu, X., & Li, X. (2012). Removal of silver nanoparticles in
simulated wastewater treatment processes and its impact on COD and NH4 reduction.
Chemosphere, 87(3), 248-252. doi:https://doi.org/10.1016/j.chemosphere.2011.12.042.
. Brown, J. (2017). Impact of Silver Nanoparticles on Wastewater Treatment. Nanotechnologies for
Environmental Remediation: Applications and Implications (pp. 255-267). Cham: Springer
International Publishing.
9. Hou, L., Li, K., Ding, Y., Li, Y., Chen, J., Wu, X., & Li, X. (2012). Removal of silver nanoparticles in
simulated wastewater treatment processes and its impact on COD and NH4 reduction.
Chemosphere, 87(3), 248-252. doi:https://doi.org/10.1016/j.chemosphere.2011.12.042.
10. Laglera L, Tovar-Sanchez A (2012). Direct recognition and quantification by volammetry of
thiol/thioamide mixes in seawater. Talanta, 89: 496-504.
11. Sidenius U, Skonberg C, Olsen J, Hansen S (2003). In vitro reactivity of carboxylic acid-CoA
thioesters with glutathione. Chemical Research in Toxicology, 17: 75-81.
12. Levard C, Hotze E, Lowry G, Brown G (2012). Environmental Transformations of Silver
Nanoparticles: Impact on Stability and Toxicity. Environmental Science & Technology, 46: 6900-
6914.
13. Choi O, Cleunger T, Deng B, Surampalli R, Ross L, Hu Z (2009). Role of sulfide and ligand strength
in controlling nanosilver toxicity. Water Research 43 (7): 1879-1886.
14. Johnston H, Cuta F, Garrett A (1933). The Solubility of Silver Oxide in Water, in Alkali and in
Alkaline Salt Solutions. The Amphoteric Character of Silver Hydroxide. Journal of the American
Chemical Society, 55: 2311-2325.
15. Gupta A, Maynes M (1998). Effects of halides on plasmid-mediated silver resistance in
Escherichia coli. Applied Environmental Microbiology, 64 (12): 5042-5045.
1 . Andryushechkin B, Eltsoc K, Shevlyuga V (2007). Local structures of thin AgCl films on silver
surface. Physics of Wave Phenomena 15 (2): 116-125.
17. Kleber C, Wiesinger R, Schnoller J, Hilfrich U, Hutter H, Schreiner M (2008). Initial oxidation of
silver surfaces by S2- and S+4 species. Corrosion Science 50 (4): 1112-1121.
1 . Adams N, Kramer J (1999). Silver speciation in wastewater effluent, surface waters and pore
waters. Environmental Toxicology Chemistry 18 (12): 2667-2673.
19. Blakelock, Graham C.; Xenopoulos, Marguerite A.; Norman, Beth C.; Vincent, Jennifer L.; Frost, Paul
C. (December 2016). "Effects of silver nanoparticles on bacterioplankton in a boreal lake" (http://d
oi.wiley.com/10.1111/fwb.12788). Freshwater Biology. 61 (12): 2211–2220.
doi:10.1111/fwb.12788 (https://doi.org/10.1111%2Ffwb.12788).
20. Vollmer W, Blanot D, Pedro M (2007). Peptidoglycan structure and architecture. Federation of
European Microbiological Societies, 32: 149-167.
21. Su-juan Y, Yong-guang Y, Jing-fu L (2013). Silver nanoparticles in the environment. Environmental
Science, 1.
22. Fabrega J, Luoma S, Tyler C, Galloway T, Lead J (2011). Silver nanoparticles: Behaviour and
effects in the aquatic environment. Environment International, 37 (2): 517-531.
23. Lannig G, Eilers S, Pörtner H, Sokolova I and Bock C. (2010). Impact of Ocean Acidification on
Energy Metabolism of Oyster, Crassostrea gigas — Changes in Metabolic Pathways and Thermal
Response. Marine Drugs 8: 2318-2339.

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