1
Emerging Patterns for Engineered Nanomaterials in the Environment:
2
A Review of Fate and Toxicity Studies
3
4
Kendra L. Garner and Arturo A. Keller
5
6
UC Center on the Environmental Implications of Nanotechnology and School of Environmental Science
and Management, University of California, Santa Barbara, CA 93106
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8
Supporting Information
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10
11
12
13
14
15
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18
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1
24
Many studies were considered for determining the merging patterns for fate and toxicity
25
represented in Figures 2-5. These sources are summarized in Table S1. Some of these sources
26
provided direct process rate information, while others provided additional conditions or
27
exceptions to the generalized results, as discussed in the main manuscript.
28
Table S1. References for rates of aggregation, sedimentation, and dissolution, as well as
29
specifically how ENMs interact with NOM, transport in porous media, and toxicity.
NP Specific References
Process
Aggregation
Rates
Adeleye et al., 2013; Afrooz et al., 2013; Aruoja et al., 2009; Baalousha,
2009; Baalousha et al., 2008; Bennett et al., 2013; Bian et al., 2011; Chen et
al., 2007, 2006, 2012; Chen and Elimelech, 2007, 2006; Chinnapongse et
al., 2011; Chowdhury et al., 2011; Cornelis et al., 2011; Delay et al., 2011;
Diedrich et al., 2012; Domingos et al., 2009; Dunphy Guzman et al., 2006;
Elzey and Grassian, 2010; Fabrega et al., 2009; Fairbairn et al., 2011; Fang
et al., 2009; Fortner et al., 2005; Franklin et al., 2007; French et al., 2009;
Furman et al., 2013; Ghosh et al., 2010; Gong et al., 2011; Griffitt et al.,
2008; He and Zhao, 2005; Hoecke et al., 2009; Hotze et al., 2010; Huynh
and Chen, 2011; Hyung et al., 2006; Jones and Su, 2012; Keller et al., 2012,
2010; T. Li et al., 2010; Li et al., 2011, 2010; Limbach et al., 2008; Lin et
al., 2010; Liu et al., 2009; Ma et al., 2013; Miller et al., 2010; Pakrashi et
al., 2012; Pelley and Tufenkji, 2008; Petosa et al., 2012; Pettibone et al.,
2008; Phenrat et al., 2007; Quik et al., 2013; Reinsch et al., 2012; N. Saleh
et al., 2008; N. B. Saleh et al., 2008; Schrick et al., 2004; Shih et al., 2012;
Simon-Deckers et al., 2009; Stankus et al., 2010; Stebounova et al., 2011;
Thio et al., 2011; Unrine et al., 2010; Velzeboer et al., 2008; von der
Kammer et al., 2010; P. Wang et al., 2008; Y. Wang et al., 2012; Wang et
al., 2011; Wong et al., 2010; Yin et al., 2012; Zhang et al., 2009, 2008;
Zhou and Keller, 2013, 2010; Zhu et al., 2012; Zook et al., 2012
Sedimentation Adeleye et al., 2013; Aruoja et al., 2009; Battin et al., 2009; Bennett et al.,
Rates
2013; Bian et al., 2011; Chen et al., 2012; Chen and Elimelech, 2006;
Chinnapongse et al., 2011; Chowdhury et al., 2011; Fairbairn et al., 2011;
Fang et al., 2009; Ferry et al., 2009; Fortner et al., 2005; Franklin et al.,
2007; Gilbert et al., 2007; Griffitt et al., 2008; He and Zhao, 2005; Hyung
and Kim, 2008; Jones and Su, 2012; Keller et al., 2010; Kennedy, et al.,
2
Dissolution
Rates
Interactions
with NOM
Zeta Potential
Fate and
Transport in
Porous Media
2008; Z. Li et al., 2010; Limbach et al., 2008; Lowry et al., 2012; Ma et al.,
2013; Mackenzie et al., 2012; Miller et al., 2010, p. 201; Montes et al.,
2012; Pettibone et al., 2008; Quik et al., 2013, 2010; N. Saleh et al., 2008;
Schrick et al., 2004; Stankus et al., 2010; Stebounova et al., 2011; Thio et
al., 2011; von der Kammer et al., 2010; P. Wang et al., 2008; Y. Wang et al.,
2012; Yin et al., 2012; Zhang et al., 2009, 2008; Zhou and Keller, 2010;
Zhou et al., 2012b; Zhu and Cai, 2012; Zhu et al., 2012, 2007
Adeleye et al., 2013; Baalousha et al., 2008; Benn and Westerhoff, 2008;
Bian et al., 2011; Blaser et al., 2008, p. 2; Blinova et al., 2010; Cornelis et
al., 2011; David et al., 2012; Diedrich et al., 2012; Dobias and BernierLatmani, 2013, p. 2; Elzey and Grassian, 2010; Fabrega et al., 2009;
Fairbairn et al., 2011; Fang et al., 2009; Franklin et al., 2007; Gaiser et al.,
2011; Griffitt et al., 2008; Hitchman et al., 2013; Ho et al., 2010; Huynh and
Chen, 2011; Judy et al., 2011; Kasemets et al., 2009; Keller et al., 2010;
Levard et al., 2011; Li et al., 2013; Li et al., 2011, 2010; Liu and Hurt, 2010;
Liu et al., 2010, 2009; Ma et al., 2013; Mahmood et al., 2011; Miller et al.,
2010; Montes et al., 2012; Mortimer et al., 2010; Pakrashi et al., 2012;
Petosa et al., 2012; Reed et al., 2012; Reinsch et al., 2012; Rimer et al.,
2007; Roelofs and Vogelsberger, 2006, 2004; Simon-Deckers et al., 2009;
Stebounova et al., 2011; Vogelsberger et al., 2008; Wang et al., 2011; Wong
et al., 2010; Xia et al., 2008; Yin et al., 2012; Zook et al., 2012
Baalousha, 2009; Baalousha et al., 2008; Bennett et al., 2013; Bian et al.,
2011; Blinova et al., 2010; Chen et al., 2012; Chinnapongse et al., 2011;
Delay et al., 2011; Fabrega et al., 2009; Franklin et al., 2007; Furman et al.,
2013; Ghosh et al., 2010; Hitchman et al., 2013; Huynh and Chen, 2011;
Hyung and Kim, 2008; Hyung et al., 2006; Jones and Su, 2012; Kennedy, et
al., 2008; Z. Li et al., 2010; Limbach et al., 2008; Liu and Hurt, 2010;
Lowry et al., 2012; Pelley and Tufenkji, 2008; Quik et al., 2010; N. B. Saleh
et al., 2008; Shoults-Wilson et al., 2011; Stankus et al., 2010; Thio et al.,
2011; von der Kammer et al., 2010; P. Wang et al., 2008; Y. Wang et al.,
2012; Wang et al., 2011; Westerhoff et al., 2013; Xie et al., 2008; Yin et al.,
2012; Zhang et al., 2009; Zhou and Keller, 2010
Adeleye et al., 2013; Battin et al., 2009; Bian et al., 2011; Delay et al., 2011;
Elzey and Grassian, 2010; French et al., 2009; Ghosh et al., 2010; Griffitt et
al., 2009, 2008; Handy et al., 2008; Hitchman et al., 2013; Jiang et al., 2009;
Judy et al., 2011; Limbach et al., 2008; Mackenzie et al., 2012; Petosa et al.,
2012; Quik et al., 2010; Reed et al., 2012; Sunkara et al., 2010; P. Wang et
al., 2008; Wang et al., 2011; Yin et al., 2012
Ben-Moshe et al., 2010; Boxall et al., 2007; Bradford et al., 2002; Brant et
al., 2005; Cheng et al., 2005; Chowdhury et al., 2011; Cornelis et al., 2010;
Darlington et al., 2009; Espinasse et al., 2007; Fang et al., 2009; Ghosh et
3
Toxicity
al., 2008; Godinez and Darnault, 2011; Grant et al., 2001; Grolimund et al.,
2001; Jaisi and Elimelech, 2009; Jaisi et al., 2008; Jeong and Kim, 2009;
Johnson et al., 2009; Jones and Su, 2012; Kanel et al., 2008; Kool et al.,
2011; Lecoanet and Wiesner, 2004; Lecoanet et al., 2004; Li et al., 2008; Z.
Li et al., 2011; Liu et al., 2009; Mattison et al., 2011; Milani et al., n.d.;
Pelley and Tufenkji, 2008; Petosa et al., 2012; Phenrat et al., 2010; N. Saleh
et al., 2008; Schrick et al., 2004; Shoults-Wilson et al., 2011; Tian et al.,
2012, 2010; Tiede et al., 2009; Tosco et al., 2012; Tourinho et al., 2012;
Tufenkji and Elimelech, 2004; Vecchia et al., 2009; C. Wang et al., 2012; Y.
Wang et al., 2012, 2008; Xiao and Wiesner, 2013
(Adams et al., 2006; Aruoja et al., 2009; Baek and An, 2011; Battin et al.,
2009; Baun et al., 2008; Ben-Moshe et al., 2013; Bennett et al., 2013;
Blinova et al., 2010; L. Canesi et al., 2010; Laura Canesi et al., 2010;
Coleman et al., 2010; Crane et al., 2008; Fabrega et al., 2009; Franklin et al.,
2007; Gaiser et al., 2011; García et al., 2011; Gomes et al., 2011; Gong et
al., 2011; Griffitt et al., 2009, 2008, 2007; Heinlaan et al., 2008; Ho et al.,
2010; Hoecke et al., 2009; Horie et al., 2013, 2009; Ji et al., 2011; Jiang et
al., 2009; Judy et al., 2011; Kadar et al., 2010; Kasemets et al., 2009; Keller
et al., 2013, 2012; Kennedy, et al., 2008; Kool et al., 2011; Li et al., 2009,
2013; M. Li et al., 2011; T. Li et al., 2010; Z. Li et al., 2010; Manabe et al.,
2011; Manzo et al., 2011; Miao et al., 2009; Miller et al., 2010; Mortimer et
al., 2010; Pakrashi et al., 2012; Parks et al., 2013; Reinsch et al., 2012;
Ringwood et al., 2009; Rogers et al., 2010; Shoults-Wilson et al., 2011;
Simon-Deckers et al., 2009; Singh et al., 2011; Tedesco et al., 2010; Tong et
al., 2007; Velzeboer et al., 2008; Wong et al., 2010; Xia et al., 2008; Zhu et
al., 2012, 2009, 2007; Zook et al., 2012)
30
31
Figure 2 in main manuscript was created using Table S2, which considers aggregation rates
32
observed in many different waters. For ENMs with multiple studies on the rates of aggregation in
33
a water type, we used the most common rate provided, meaning that if two sources estimated the
34
rate of aggregation as days and one sources as weeks, we put days, and noted in the footnotes
35
that the third source estimated weeks. Red indicates aggregation within hours, orange indicates
36
aggregation within days, yellow indicates aggregation within weeks, and green indicates minimal
37
aggregation over months or longer. These categorizations are solely with respect to the rate of
38
aggregation without evaluating exposure or risk. Key details, deviations and exceptions are noted
39
in the footnotes. Asterisks indicate the presence of a coating on the ENMs.
4
40
Table S2. Aggregation rates by water type
NP
Stormwater (low IS, high
NOM)
Fabrega et al., 2009; Huynh
and Chen, 2011*;
Chinnapongse et al., 2011*
Freshwater (low IS, mid
NOM)
Fabrega et al., 2009;
Huynh and Chen, 2011*;
Chinnapongse et al., 2011*
Al2O3
Au
Stankus et al., 2010*
Pakrashi et al., 2012
Stankus et al., 2010*; Li et
al., 2010
CeO2
Keller et al., 2010
Ag
Keller et al., 2010;
Cornelis et al., 2011*;
Adeleye and Keller, 2014;
Chen and Elimelech, 2007
FeOOH
FeO/Fe2O3
Latex
MWCNTs
NiO
nZVI
Seawater (high IS, low
NOM)
Li et al., 20111;
Chinnapongse et al.,
2011*2
Unrine et al., 2010; Afrooz
et al., 2013*3; Stankus et
al., 2010*
Keller et al., 2010
Afrooz et al., 2013*
Keller et al., 2010; Hoecke
et al., 2009
Jones and Su, 20124
CuO
C60
Groundwater (mid IS, low
NOM)
Huynh and Chen, 2011*;
Chinnapongse et al., 2011*
Adeleye and Keller,
2014; Chen and Elimelech,
Adeleye and Keller,
20145; Fortner et al., 2005;
Adeleye and Keller,
20146; Chen and
2007
Chen and Elimelech, 2007
Elimelech, 2006; Fortner
et al., 2005; Chen and
Elimelech, 2007
Gilbert et al., 20078
Chen et al., 2006*
Baalousha, 2009
Baalousha, 2009
Saleh et al., 2008
Saleh et al., 2008*
Saleh et al., 2008
Gong et al., 2011
Keller et al., 2012*11
SiO2
Zhang et al., 2009
Zhang et al., 2009
SWCNTs
TiO2
Bennett et al., 2013; Wang
et al., 2008
Domingos et al., 2009; von
der Kammer et al., 2010;
Shih et al., 2012
Bennett et al., 2013; Wang
et al., 2008
Velzeboer et al., 200812;
Keller et al., 2010; Thio et
al., 2011; Domingos et al.,
2009; von der Kammer et
al., 2010; Shih et al., 2012
ZnO
Zhou and Keller, 2010
Zhou and Keller, 2010;
Keller et al., 2010;
Franklin et al., 200714
Gilbert et al., 20077
Zhang et al., 2008
Pelley and Tufenkji, 2008
Lin et al., 20109
Zhang et al., 2008
Keller et al., 2012*; Yin et
al., 2012
Zhang et al., 2009; Zhang
et al., 2008
Bennett et al., 2013
Thio et al., 2011; Zhang et
al., 2008; French et al.,
200913; Chen et al., 2012;
von der Kammer et al.,
2010; Shih et al., 2012
Zhou and Keller, 2010;
Zhang et al., 200815; Bian
et al., 2011
Lin et al., 201010
Keller et al., 2012*; Yin et
al., 2012*
Zhang et al., 2009
Bennett et al., 2013
Keller et al., 2010;
Chowdhury et al., 2011;
Domingos et al., 2009;
French et al., 2009; Chen
et al., 2012; von der
Kammer et al., 2010;
Simon-Deckers et al.,
2009; Shih et al., 2012
Zhou and Keller, 2010;
Keller et al., 2010; Miller
et al., 2010; Fairbairn et
1
Aggregation of coated Ag is on the order of weeks at IS below 400 mMol NaCl
Aggregation of Ag in seawater occured within hours
3
Coated Au aggregates within hours in the presence of common groundwater cations
4
Aggregation of CuO in groundwater ranges from days to weeks
5
Significant C60 aggregation occurs within hours in groundwater
6
Significant C60 aggregation occurs within hours in seawater
7
Tests completed at g/L concentrations
8
Tests completed at g/L concentrations
9
Tests completed at 200 mg/L
10
Tests completed at 200 mg/L
11
Uncoated nZVI will aggregate within minutes in freshwater
12
No significant aggregation of TiO2 occurred in pond water over the course of weeks
13
TiO2 aggregates in hours in the presence of any IS
14
ZnO aggregates within 6 hours for in freshwater
2
5
al., 2011; Bian et al., 2011;
Wong et al., 2010
41
Figure 3 in the main manuscript was created using the Table S3, which considers sedimentation
42
rates observed in different studies. Colors follow Table S2. Categorizations do not evaluate
43
exposure or risk. Key details, deviations and exceptions are noted in the footnotes.
44
Table S3. Sedimentation rates by water type
NP
Stormwater (low IS, high
NOM)
Freshwater (low IS, mid
NOM)
Ag
Chinnapongse et al., 2011*
Lowry et al., 2012;
Groundwater (mid IS, low
NOM)
Stebounova et al., 2011*;
Chinnapongse et al., 2011*; Quik
et al., 2013*16
Chinnapongse et al., 2011*;
Au
CeO2
Stankus et al., 2010*
Keller et al., 2010; Quik et
al., 2010; Limbach et al.,
2008
CuO
C60
Adeleye and Keller, 2014;
Fortner et al., 2005; Zhu and
Cai, 2012;
FeOOH
FeO/Fe2O3
MWCNTs
Seawater (high IS, low NOM)
Griffitt et al., 2008; Quik et
al., 2013*
Stankus et al., 2010*
Keller et al., 201017; Zhou et
al., 2012; Quik et al., 2010;
Quik et al., 2013
Stankus et al., 2010*
Keller et al., 2010
Ferry et al., 2009
Keller et al., 2010; Fairbairn et
al., 2011 ; Montes et al., 2012;
Quik et al., 2010; Limbach et al.,
2008; Quik et al., 201318
Griffitt et al., 2008
Adeleye and Keller, 2014;
Fortner et al., 2005; Zhu and
Cai, 2012; Quik et al.,
201319
Adeleye and Keller,
201420; Fortner et al., 2005;
Zhu and Cai, 2012
Adeleye and Keller, 201421;
Chen and Elimelech, 2006;
Fortner et al., 2005; Zhu and Cai,
2012; Quik et al., 2013
Gilbert et al., 2007
Zhang et al., 2008
Gilbert et al., 2007
Zhu et al., 2012
22
Wang et al., 2008; Hyung
Wang et al., 2008; Hyung and
and Kim, 2008; Hyung et
al., 2006; Lin et al., 2010
NiO
nZVI
Schrick et al., 2004*
Kim, 2008; Hyung et al.,
2006; Lin et al., 2010
Griffitt et al., 2008
Schrick et al., 2004*
SiO2
Zhang et al., 2009
Zhang et al., 2009
SWCNTs
TiO2
Wang et al., 2008
Keller et al., 2010; Wang et
al., 2012; von der Kammer
et al., 2010
Wang et al., 2008
Keller et al., 2010; Zhou et
al., 201225; Wang et al.,
Zhu and Cai, 2012; Hyung and
Kim, 2008; Lin et al., 2010
Zhang et al., 2008
Li et al., 2010*; Saleh et
al., 2008*
Li et al., 2010; Yin et al.,
2012*23
Zhang et al., 2009; Zhang
et al., 200824
Zhang et al., 2009
Keller et al., 2010; Zhang et
al., 2008; Chen et al., 2012;
Keller et al., 2010; Fairbairn et
al., 2011; Chen et al., 2012
15
ZnO aggregates within days in tap water
Ag will sediment over the course of weeks to months
17
CeO2 sedimentation takes more than weeks in freshwater
18
CeO2 sediments in seawater over the course of days to weeks
19
C60 sediments within days in freshwater
20
Significant sedimentation of C60 occurred within 8 days
21
Some C60 was still found in seawater after 8 days, indicating sedimentation over the course of weeks
22
Uncoated Fe2O3 settles within days in zebrafish culture medium
23
Coated nZVI sedimented in the presence of IS over the course of hours
24
SiO2 sediments over the course of weeks in tap water
25
TiO2 sediments over weeks in low IS freshwater
16
6
ZnO
2012; von der Kammer et al.,
2010; Battin et al., 200926
Zhou and Keller, 2010; Keller
et al., 201028; Zhou et al.,
2012; Franklin et al., 200729
Keller et al., 2010;
Fang et al., 200927; von
der Kammer et al., 2010
Keller et al., 2010; Zhang et
al., 200830
Zhou and Keller, 2010; Keller et
al., 2010; Miller et al., 201031;
Fairbairn et al., 2011
45
Figure 4 on dissolution rates was created using the studies in Table S4. Red indicates dissolution
46
within hours, orange indicates dissolution within days, yellow indicates dissolution within
47
weeks, and green indicates minimal dissolution over months or longer. These categorizations do
48
not evaluate exposure or risk. Key details, deviations and exceptions are noted in the footnotes.
49
Asterisks indicate the presence of a coating on the ENM.
50
Table S4. Dissolution rates by water type
NP
Stormwater (low IS,
high NOM)
Freshwater (low IS, mid NOM)
Dobias and Bernier-Latmani,
2013*32; Fabrega et al., 2009; Huynh
and Chen, 2011*; Griffitt et al., 2008;
Gaiser et al., 2011; Quik et al.,
2013*33
Griffitt et al., 2008; Pakrashi et al.,
Ag
Groundwater (mid IS,
low NOM)
Shoults-Wilson et al.,
2011*; Liu and Hurt,
2010*; Benn and
Westerhoff, 2008
Hitchman et al.,
2013*36
Hitchman et al., 2013*
Cornelis et al., 2011*; Gaiser et al.,
Wang et al., 2011
CuO
FeO/ Fe2O3
NiO
nZVI
PbS
TiO2
Baalousha et al., 2008
Mahmood et al.,
201137
Unrine et al., 2010;
and Vogelsberger, 2006
Hitchman et al., 2013*
Hitchman et al.,
2013*; Judy et al.,
2011*
Au
CeO2
Liu and Hurt, 2010*34; Li et al.,
2010*; Quik et al., 2013*35
Simon-Deckers et al., 2009; Roelofs
2012
Al2O3
Seawater (high IS, low NOM)
2011; Quik et al., 2013
Blinova et al., 2010; Aruoja et al.,
2009; Griffitt et al., 2008; Wang et al.,
2011; Mortimer et al., 2010
Baalousha et al., 2008
Griffitt et al., 2008; Mahmood et al.,
2011
Cornelis et al., 2011*
Wang et al., 2011
Montes et al., 2012; Quik et al.,
2013
Wang et al., 2011
Mahmood et al., 2011
Mahmood et al., 2011
Adeleye et al., 2013*
Liu et al., 2009
Keller et al., 2010;
Miller et al., 2010; Griffitt et al., 2008
Keller et al., 2010;
Keller et al., 2010; Miller et al.,
26
TiO2 sediments within hours in natural lake water
TiO2 sediments in days to weeks in soil water
28
ZnO did no aggregate in 8 hours in freshwater
29
ZnO sedimentation occurred with 6 hours in freshwater
30
ZnO sedimented in tapwater within days
31
ZnO sediments in seawater within hours at ZnO concentrations above 10 mg/L, but may take a week at lower
concentrations
32
In river water, only half of the coated Ag dissolved over four months
33
Coated Ag dissolution may take months in freshwater
34
Ag dissolved in seawater between 6 and 125 days
35
Coated Ag dissolution in seawater will take from weeks to months
36
PVP-stabilized Au is essentially insoluble in all media
37
NiO dissolution is negligible between pH7-11, even in presence of salts for all media
27
7
Miller et al., 2010
Miller et al., 2010
Li et al., 2013
Li et al., 2013; Bian et al., 2011;
Blinova et al., 201038; Franklin et al.,
2007; Reed et al., 2012; Mortimer et
al., 2010
ZnO
Reed et al., 2012; Kool
et al., 2011;
2010
Miller et al., 2010; Fairbairn et al.,
2011; Li et al., 2013; Wong et al.,
2010; Xia et al., 2008; Montes et
al., 201239; David et al., 2012
51
52
Table S5 includes a summary of toxicity tests for various ENMs on various species in different
53
media. Toxicity observed at environmentally relevant concentrations are highlighted in red.
54
Toxicity observed at environmentally relevant concentrations if they were to increase 100-fold
55
are highlighted in orange. Toxicity observed at < 10 mg/L are highlighted in yellow. Minimal
56
toxicity observed at concentrations > 10 mg/L are highlighted in light green. When no toxicity
57
was observed at all tested concentrations, the cells are highlighted in dark green. White indicates
58
that not enough data were given to place the study into one of the above categories. Asterisks
59
indicate the presence of a coating on the ENM.
60
Table S5. Toxicity of ENMs to various species.
NP
Species
Ag
Ag
E. coli
Hemolytic toxicity
Ag
P. fluorescens
Ag
E. fetida
Ag
E. coli
Ag
Ag
D. magna
D. pulex, D. rerio, P.
kirchneriella
Ag
D. magna
38
39
Toxic Concentration
Minimum inhibitory concentration 100 μM
All AgNPs caused at least 75% hemolysis at the highest
concentration of 100 ug/ml, and caused no additional
hemolysis compared to the
DMEM at the lowest concentration of 10 ug/ml.
Ag reduced bacterial growth entirely at 2000 ppb (19
μM) under all conditions and adversely affected growth
at 200 ppb (1.9 μM) under some conditions, indicating
some toxicity
Toxicity observed at 7.41 mg/kg in sandy loam soil
Dissolved Ag concentrations measured in the E. coli
growth inhibition media with AgNP concentrations equal
to 50 mg/L were 8−10 μg/L for the unsulfidized and
lowest sulfidized AgNP (agg) samples
LC50 ~ 3 ug/L
LC50 0.04-7.2 mg/L
Acute toxicity 56% death at 0.1 mg/L, 100% death at 1
mg/L, chronic toxicity at 0.001 mg/L
Reference
Ho et al., 2010*
Zook et al., 2012*
Fabrega et al., 2009
Shoults-Wilson et
al., 2011*
Reinsch et al., 2012*
Li et al., 2010
Griffitt et al., 2008
Gaiser et al., 2011
ZnO at 10 mg/L dissolved over hours to days
ZnO at concentrations below 10 mg/L dissolves over the course of days
8
Species
Toxic Concentration
Ag
NP
Thalassiosira weissflogii
Miao et al., 2009
Al2O3
Microtox (bacteria),
pulse-amplitude
modulation (algae),
Chydotox (crustaceans),
and Biolog (soil
enzymes)
C. metallidurans CH34
and E. coli MG1655
B. subtilis, E. coli and P.
fluorescens
D. magna
D. pulex, D. rerio, P.
kirchneriella
Photosynthesis and chlorophyll were severely suppressed
beyond around 1*10^-11 M.
No effects were observed up to 100 mg/L
Toxic at all concentrations (10 – 500 mg/L)
Simon-Deckers et al.,
2009
36-70% of bacteria died at 20 mg/L
Jiang et al., 2009
EC50 ~114.357 mg/L, LC50 ~162.392
LC50 3.99 - >10 mg/L
Zhu et al., 2009
Griffitt et al., 2008
No mortality occurred in subchronic exposures, although
reproduction decreased at ≥3,000 mg/kg nano-sized
Al2O3
Bioavalable and reproduction was negatively affected at
8 and 3.4% of bulk soil concentrations
LC50 ~ 70 mg/L
biomagnification factor 6.2 - 11.6
Oxidative stress occurred within 24 hours at 750 ppb
No effects were observed up to 100 mg/L
Coleman et al., 2010
No acute toxicity was observed for the two crustaceans
and D.rerio embryos, up to test concentrations of 1000,
5000, and 200
mg/L, respectively. In contrast, significant chronic
toxicity to P. subcapitata with EC10s between 2.6-5.4
mg/L was observed.
CeO2 (25 ug/mL) NPs were taken up intact the cells
without inflammation or cytotoxicity
LC50 ~0.012 mg/ml
LC50 10.3 mg/L
No acute toxicity. Chronic toxicity at 10 mg/L
As the concentration of Cr2O3 (100 nm) in the culture
media increased from 0 – 100 ug/mL, the percentage of
live cells decreased linearly
Hoecke et al., 2009
HaCaT cells showed a greater reduction in cell viability
by Cr2O3 exposure than A549 cells. In particular, the
cytotoxicity of NPs was
higher than that for fine particles at a high concentration
of Cr2O3 (0.5 mg/mL)
LC50 1.56 mg/L
The L (E)C50 values of nanoCuO for both crustaceans in
natural water ranged from 90 to 224 mg Cu/l
EC50 = 0.71 mg Cu/l
Horie et al., 2013
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
E. fetida
Au
E fetida
Au
Au
Au
CeO2
D. magna
M. sexta
Mytilus edulis
Microtox (bacteria),
pulse-amplitude
modulation (algae),
Chydotox (crustaceans),
and Biolog (soil
enzymes)
P. subcapitata, D.
magna, and T. platyurus,
and embryos of D. rerio
CeO2
CeO2
CeO2
CeO2
CeO2
Cr2O3
RAW 264.7 and BEAS2B cell lines
D. magna
P. subcapitata
D. magna
E. coli
Cr2O3
Human lung carcinoma
A549 cells and human
keratinocyte HaCaT cells
Cu
CuO
D. rerio
D. magna, T. platyurus,
and T. thermophila
P. subcapitata
CuO
Reference
Velzeboer et al., 2008
Unrine et al., 2010
Li et al., 2010
Judy et al., 2011*
Tedesco et al., 2010
Velzeboer et al., 2008
Xia et al., 2008
García et al., 2011
Rogers et al., 2010
Gaiser et al., 2011
Singh et al., 2011
Griffitt et al., 2007
Blinova et al., 2010
Aruoja et al., 2009
9
Species
Toxic Concentration
CuO
NP
Soil microbe community
Chen et al., 2006
CuO
E. coli, B. subtilis, and S.
aureus
V. fischeri, D. magna,
and T. platyurus
D. pulex, D. rerio, P.
kirchneriella
soil microbe community changed, indicating toxicity at 1
and 5% w/w dry soil
EC50 ranged from 28.6 – 65.9 mg/L
L (E)C59 ~ 2.1 – 79 mg/L
Heinlaan et al., 2008
LC50 0.06 - 0.94 mg/L
Griffitt et al., 2008
8-h EC50 were 20.7 mg/L and 24-h EC50 were 13.4
mg/L
EC50 128 mg/L
Kasemets et al.,
2009
Mortimer et al.,
2010
Gomes et al., 2011
CuO
CuO
CuO
S. cerevisiae
CuO
T. thermophila
CuO
Mytilus galloprovincialis
C60
Microtox (bacteria),
pulse-amplitude
modulation (algae),
Chydotox (crustaceans),
and Biolog (soil
enzymes)
P. subcapitata and D.
magna
C60
C60
D. rerio
C60
C60
C60
D. magna
Soil microbe community
Crassostrea virginica
C60
Fe2O3
Fe2O3
Mytilus galloprovincialis
D. rerio
Mytilus galloprovincialis
Fe3O4
Soil microbe community
Fe3O4
Latex
MWCNTs
D. magna
O. latipes
C. metallidurans CH34
and E. coli MG1655
C. dubia, L. plumulosus
and H. azteca
MWCNTs
MWCNTs
NiO
D. magna
C. vulgaris
NiO
E. coli, B. subtilis, and S.
CuO NPs induced oxidative stress in mussels by
overwhelming gills antioxidant defense system at 10
ug/L
Toxic effects were observed at greater than 1 mg/L
The mobility of daphnids was not affected in the tested
concentrations (≤50 mg C60/l). The algal growth rate was
inhibited up to 30% at 90 mg C60/l, but no reproducible
concentration–response relationships could be
established
C60 at 1.5 mg/L delayed zebrafish embryo and larval
development
EC50 ~9.344 mg/L and LC50 ~ 10.515 mg/L
No effect on structure, function, or processes
Significant toxicity at 10 ppb
Some effects observed at 5 mg/L
EC50 ~ 36.06 mg/L, LC50 ~ 53.35mg/L
no significant effect was detected following exposure of
embryos to Fe up to 8 mg/L
minimal changes to microbial community, indicating
limited toxicity at 1 and 5% w/w dry soil
LC50 ~23·10-4 mg/ml
Survival decreased under some conditions at 1 mg/L
50 – 60% viability loss at 100 mg/L
Reference
Baek and An, 2011
Velzeboer et al., 2008
Baun et al., 2008
Zhu et al., 2007
Zhu et al., 2009
Tong et al., 2007
Ringwood et al.,
2009
Canesi et al., 2010
Zhu et al., 2012
Kadar et al., 2010
Chen et al., 2006
García et al., 2011
Manabe et al., 2011
Simon-Deckers et al.,
2009
Aqueous exposures to raw MWNTs decreased C. dubia
viability, but such effects were not observed during
exposure to functionalized MWNTs (>80 mg/L).
Sediment exposures of the amphipods indicated
mortality increased as particle size decreased, although
raw MWNTs induced lower mortality (LC50 50 to >264
g/kg) than carbon black (LC50 18–40 g/kg) and activated
carbon (LC50 12–29 g/kg).
EC50 ~8.723 mg/L and LC50 ~22.751 mg/L
NiO NPs had severe impacts on the algae, with 72 h
EC50 values of 32.28 mg NiO/L
Kennedy, et al.,
2008
EC50 ranged from 121.1 – 160.2 mg/L
Baek and An, 2011
Zhu et al., 2009
Gong et al., 2011
10
NP
NiO
NiO
Species
aureus
Human keratinocyte
HaCaT cells, Human
lung carcinoma A549
cells
D. pulex, D. rerio, P.
kirchneriella
Toxic Concentration
Reference
The cell proliferation was completely inhibited by 50
μg/mL Ni2+
Horie et al., 2009
LC50 0.35 - >10 mg/L
Griffitt et al., 2008
nZVI
I. galbana, D. tertiolecta,
T. pseudonana, P.
subcapitata, and D.
magna
Growth was suppressed between 0.4 and 12 mg/L
Keller et al., 2012*
nZVI
E. coli
Li et al., 2010*
nZVI
Sb2O3
O. latipes
E. coli, B. subtilis, and S.
aureus
B. subtilis and E. coli
Minimum inhibitory concentration (MIC) after 24 h was
5 mg/L for uncoated nZVI. MIC for coated nZVI ranged
from 100-500 mg/L
Toxicity observed at 0.5 mg/L
EC50 ranged from 144.7 – 324 mg/L
SiO2 at 5000 mg/L resulted in 99% growth reduction of
B. subtilis, but only 48% growth reduction of E. coli at
5000 mg/L
40-70% of bacteria died at 20 mg/L
Adams et al., 2006
Some negative effects at 10 mg/L
No effect observed up to 5 mg/L
No toxic effect observed up to 1000 mg/L
Exposure to 10 mg/L CNT does negatively influence the
growth of algae across most treatments. However,
decreased growth was observed compared with the
control.
EC50 ~1.306 mg/L and LC50 ~2.425 mg/L
No significant mortality to any species via sediment or
food matrices was observed at concentrations up to
100 ppm.
No effects were observed up to 100 mg/L
Canesi et al., 2010
Canesi et al., 2010
Ji et al., 2011
No toxic effects up to g/L concentrations
Miller et al., 2010
72% growth reduction in E. coli exposed to 5000 mg/L
and 75% growth reduction in B. subtilis exposed to 1000
mg/L
Significant loss of viability was observed after exposure
to the smallest TiO2 NP (10 to 25 nm) and viability
decreased from 15-52% at 100 mg/L.
TiO2 (25 ug/mL) did not elicit any adverse or protective
effects
EC50=5.83 mg Ti/l
24 h of exposure nano-TiO2 (initial concentration,
5.3mgL-1) had significantly damaged cell membranes.
Adams et al., 2006
SiO2
SiO2
SiO2
SiO2
SiO2
SWCNTs
B. subtilis, E. coli and P.
fluorescens
Mytilus galloprovincialis
Mytilus galloprovincialis
Chlorella sp.
P. subcapitata
SWCNTs
SWCNTs
D. magna
A. abdita, A. bahia, L.
plumulosus
TiO2
Microtox (bacteria),
pulse-amplitude
modulation (algae),
Chydotox (crustaceans),
and Biolog (soil
enzymes)
T. pseudonana, and S.
marinoi, D. tertiolecta
and I. galbana
B. subtilis and E. coli
TiO2
TiO2
TiO2
C. metallidurans CH34
and E. coli MG1655
TiO2
RAW 264.7 and BEAS2B cell lines
P. subcapitata
Phytoplankton and
Biofilms
TiO2
TiO2
Li et al., 2009*
Baek and An, 2011
Jiang et al., 2009
Bennett et al., 2013
Zhu et al., 2009
Parks et al., 2013
Velzeboer et al., 2008
Simon-Deckers et al.,
2009
Xia et al., 2008
Aruoja et al., 2009
Battin et al., 2009
11
NP
TiO2
TiO2
TiO2
TiO2
TiO2
TiO2
Species
B. subtilis, E. coli and P.
fluorescens
V. fischeri, D. magna,
and T. platyurus
D. rerio
D. magna
D. magna
D. pulex, D. rerio, P.
kirchneriella
Toxic Concentration
Reference
Similar, but less damaging effects were observed in
biofilms
TiO2 NPs did not affect bacterial populations
Jiang et al., 2009
Not toxic even at 20 g/L
Heinlaan et al., 2008
Not toxic up to 100 mg/L
EC50 ~ 35.306 mg/L and LC50 ~ 143.387 mg/L
LC50 ~0.016 mg/ml
LC50 >10 mg/L
Griffitt et al., 2009
Zhu et al., 2009
García et al., 2011
Griffitt et al., 2008
TiO2
S. cerevisiae
Not toxic even at 20000 mg/L
Kasemets et al.,
2009
ZnO
T. pseudonana, and S.
marinoi, D. tertiolecta
and I. galbana
E. coli
NEC 428 μg L-1 for S. marinoi, 233 μg L-1 for T.
pseudonana. NEC for other two species around 500 1000 μg L-1.
Toxic in soft water at 1.2 mg/L, no toxicity observed at
100 mg/L in hard water
96 hour LC50 values ranged from 0.85 – 4.56 mg/L
Miller et al., 2010
At 10 mg/L, ZnO resulted in 90% growth reduction of B.
subtilis but only 48% growth reduction in E. coli resulted
at 1000 mg/L ZnO
L (E)C50 values for nanoZnO were 1.1–16 mg Zn/l
Adams et al., 2006
72-h LC50 value near 60 μg Zn/L, attributable solely to
dissolved zinc
ZnO (25 ug/mL) induced toxicity in both cells, leading to
the generation of reactive oxygen species (ROS), oxidant
injury, excitation of inflammation, and cell death.
72 h EC50 ~0.04 mg Zn/l
E50 ranged from 85.5 - >125 mg/L
Franklin et al., 2007
All media exhibited strong toxicity with 3 h LC50 at
lower than 0.1 mg Zn L-1.The bacterial
mortality all exceeded 90% at concentrations of zinc
higher than 1.0 mg L-1
All bacteria died at 20 mg/L
M. Li et al., 2011
L (E)C 50 ~ 0.18 – 3.2 mg/L
Heinlaan et al., 2008
EC50 ~ 0.622 mg/L and LC50 ~1.511 mg/L
Zhu et al., 2009
8-h EC50 121–134 mg ZnO/l and 24-h EC50 131–158
mg/l
EC50 5 mg/L
Kasemets et al.,
2009
Mortimer et al.,
2010
Kool et al., 2011
ZnO
ZnO
S. costatum, T.
pseudonana,
Li et al., 2013
Wong et al., 2010
T. japonicas, E. Rapax,
and O. melastigma
ZnO
B. subtilis and E. coli
ZnO
D. magna, T. platyurus,
and T. thermophila
P. subcapitata
ZnO
ZnO
RAW 264.7 and BEAS2B cell lines
ZnO
ZnO
P. subcapitata
E. coli, B. subtilis, and S.
aureus
E. coli
ZnO
ZnO
ZnO
B. subtilis, E. coli and P.
fluorescens
V. fischeri, D. magna,
and T. platyurus
D. magna
ZnO
S. cerevisiae
ZnO
T. thermophila
ZnO
F. candida
ZrO2
Microtox, algae,
ZnO
No effect up to 6400 mg/kg. Reproduction was affected
at just under 2000 mg/kg
No effects were observed up to 100 mg/L
Blinova et al., 2010
Xia et al., 2008
Aruoja et al., 2009
Baek and An, 2011
Jiang et al., 2009
Velzeboer et al., 2008
12
NP
Species
Toxic Concentration
Reference
Chydotox, and Biolog
61
62
63
64
65
66
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