Chemosphere 169 (2017) 437e442

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Amine-functionalized, multi-arm star polymers: A novel platform for

removing glyphosate from aqueous media
Lianna Samuel*, Ran Wang, Geraud Dubois, Robert Allen, Rudy Wojtecki, Young-Hye La**
IBM Almaden Research Center, 650 Harry Road, San Jose, CA 95120, USA

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Bioaccumulation of glyphosate
ingested in even trace amounts can
negatively impact health.

Rapid, efficient glyphosate adsorp-
tion by mesoporous-like star-poly-
mers with high amine functional
group aerial density.

Ionic interactions which promote
adsorption are affected by pH.

Glyphosate removal efficiency is
greater than 85% for neutral and
slightly basic conditions.

Maximum glyphosate adsorption ca-
pacity is 229.017 mg glyphosate/g
star-polymer.

a r t i c l e i n f o a b s t r a c t :

Article history: We describe a novel method for efficiently removing glyphosate from aqueous media via adsorption onto
Received 12 August 2016 highly functionalized star-shaped polymeric particles. These particles have a polystyrene core with more
Received in revised form than 35 attached methacrylate polymer arms, each containing a plurality of pendant amines (poly(-
8 November 2016
dimethylamino ethyl methacrylate): PDMAEMA) that are partially protonated in water. Kinetic studies
Accepted 10 November 2016
demonstrate that these star-polymers successfully remove up to 93% of glyphosate present in aqueous
solution (feed concentration: 5 ppm), within 10 min contact time, outperforming activated carbon,
Handling Editor: Shane Snyder which removed 33% after 20 min. On these star-polymers, glyphosate adsorption closely follows the
Langmuir model indicating monolayer coverage at most. Ionic interaction between the protonated
Keywords: amines and glyphosate's dissociated carboxylic and phosphoric acid groups lead to effective glyphosate
Glyphosate removal capture even at feed concentrations below 1 ppm. Surface charge of these star polymers and dissociation
Star polymer of glyphosate are both influenced by pH, thus glyphosate removal efficiency increases from 63% to 93%
Adsorption when pH increases from 4.2 to 7.7. NMR studies conducted with butylamine as a proxy for these poly-
Functionalized nanomaterials
meric particles confirm that the amine group binds with both glyphosate's carboxylic and phosphoric
Water purification
acid groups when its concentrations are in a 2:1 or higher molar ratio with glyphosate.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction

Population growth has driven the increased use of pesticides

* Corresponding author.
** Corresponding author.
and herbicides in agriculture globally, to ensure adequate food
E-mail addresses: samuell@us.ibm.com (L. Samuel), yna@us.ibm.com (Y.-H. La). supply. Glyphosate [Ne(phosphonomethyl) glycine] is the active

http://dx.doi.org/10.1016/j.chemosphere.2016.11.049
0045-6535/© 2016 Elsevier Ltd. All rights reserved.
438 L. Samuel et al. / Chemosphere 169 (2017) 437e442
ingredient of a broad spectrum, nonselective, post-emergence
herbicide. This herbicide is one of the most widely used in the
world, controlling the growth of various weeds and grasses (Guo
et al., 2005), which can stifle the development of desirable crops,
reducing both the quantity and quality of harvests. Glyphosate
usage has been largely enhanced by the use of genetically modified
crops that are glyphosate-resistant and promote its direct appli-
cation to these crops as well as targeted weeds and grasses. This
widespread use of glyphosate has led to its presence and one of its
major metabolite aminomethylphosphonic acid (AMPA) in the
environment due to run-off (both during and after its application
due to leaching).
Additionally, any applied glyphosate that remains on the har-
vested crops can be transferred to consumer products by contam-
ination of processing machinery used during their preparation.
Thus, traces of glyphosate and AMPA can be found not only in
natural waterways but also on fruits and produce available for
human consumption (Solomon and Thompson, 2003; Relyea, 2005;
Buffin and Jewell, 2014). The presence of glyphosate (in various
herbicide formulations) and its metabolite in both our food and
drinking water supplies has raised many concerns (Freuze et al.,
2007; Ho and Cherry, 2009; Qian et al., 2009; Paganelli et al.,
2010). As an herbicide, glyphosate disrupts the shikimate
pathway from amino acid biosynthesis in plants (Scho € nbrunn et al.,
2001). However, it has also been found to negatively affect enzyme
activity (Freuze et al., 2007), cause cytotoxicity and DNA damage in
human cells (Gasnier et al., 2009; Paganelli et al., 2010) and damage
to the mammalian endocrine system with prolonged exposure
(Richard et al., 2005).
Globally, the allowable concentration of glyphosate in drinking
water ranges from 0.1 mgL1 (European Union Drinking Water
Regulations, for all pesticides) (European Commission, 1991) to
0.7 mgL1 (Environmental Protection Agency drinking water
regulatory guidelines) (EPA webpage, accessed 2015). More
recently, the World Health Organization announced that glypho-
sate is a likely carcinogen to humans, as well (Fritschi et al., 2014).
Additionally, prolonged exposure to and ingestion of glyphosate
even in trace amounts (10 mg/L) has been shown to have devas-
tating effects on kidney health when combined environmental
factors such as water hardness and nephrotoxic metals
(Jayasumana et al., 2014). Therefore, there is a need to minimize the
amount of glyphosate present in drinking water and other food
products. However, glyphosate has small molecular weight, high
polarity and solubility in water although it is insoluble in organic
solvents (Stalikas and Konidari, 2001), making its removal from
aqueous solution difficult. Currently, numerous techniques (chlo-
rination, ozonation, photolysis and heterogeneous photocatalysis)
are used to reduce glyphosate concentrations in drinking water,
either individually or in different combinations (Speth, 1993;
Assalin et al., 2009). Obtaining an efficient, affordable method for
glyphosate removal is still needed (Hu et al., 2011). Adsorption can
be an affordable removal method but most activated carbon,
although used in generic water treatment because of their high
micro-porosity and degree of surface reactivity are less effective on
acidic, hydrophilic and highly soluble compounds like glyphosate
(Hamerlinck et al., 1994; Mohan and Pittman, 2006; Bozkaya-
Schrotter et al., 2008).
Stareshaped polymers provide a potential solution, they are
structurally designed to exhibit high adsorption capacity, with a
large number of arms that can be functionalized and fine-tuned to
capture specific molecules and form highly microporous structures
(Mishra and Kobayashi, 1999). In this work, batch adsorption
equilibrium study has been conducted to examine the potential use
of in-house prepared, tailored star-polymer particles with high
aerial density of amine functional groups and mesoporous-like
structure for successfully removing low concentrations of glypho-
sate from aqueous media. To better understand the relationship of
material structure and glyphosate removal efficacy, comparative
adsorption studies were also performed with polyamidoamine
(PAMAM) dendrimer with numerous amine-functional groups in
its terminal positions along with activated carbon (control). Addi-
tionally, the adsorption mechanism was also investigated together
with the influence of pH, and feed concentration on the overall
glyphosate removal efficiency of the star polymer.
2. Experimental (materials and methods)
Batch glyphosate adsorption tests were carried out with the
amine-functionalized star polymer (SP-PDMAEMA), PAMAM den-
drimers (PAMAM6) with ethylenediamine core (generation 6.0,
Sigma-Aldrich, WI, USA), and activated carbon (100 mesh, pow-
der) (Sigma-Aldrich, WI, USA) to investigate the importance of
adsorbent structure, chemistry and amine-functional density on
glyphosate adsorption. SP-PDMAEMA consists of a hydrophobic
core made up of cross-linked polystyrene and hydrophilic meth-
ylacrylate polymer arms with a plurality of tertiary amines (ex. Poly
(N, N-dimethylaminoethyl methacrylate): PDMAEMA) (Fig. 1(a)).
The polymer was synthesized via the procedure described in an
earlier literature (Lee et al., 2011).
A 10 ppm stock solution of glyphosate was made by dissolving
0.01 g of analytical grade glyphosate powder (Sigma-Aldrich, Pes-
tanal®) in 1 L deionized water (made in house, via reverse osmosis
with resistivity of 18.4 million ohm-cm and TDS: ~7 ppm). 250 ml of
the glyphosate stock solution was added to 250 ml of deionized
water to create a desired initial concentration of 5 ppm. 10 ml ali-
quots of the 5 ppm glyphosate solution were then placed into a
series of 25 ml vials containing 0.005 g of activated carbon, 0.125 ml
PAMAM6 dendrimers (5% weight dendrimers in methanol) and
5 ml SP-PDMAEMA solution (0.1% weight SP-PDMAEMA by vol-
ume), respectively, to ensure that the same mass of adsorbent was
used for each trial. Each trial was repeated four times and the
glyphosate concentrations measured were averaged. For each trial,
blank deionized water specimens were collected. The adsorption of
glyphosate onto SP-PDMAEMA, PAMAM6 and activated carbon was
then determined as a function of time and adsorption kinetics
determined.
Duplicate studies to determine the effect of pH and initial
glyphosate concentration were also conducted using SP-
PDMAEMA, to better understand its efficiency. PAMAM6 was not
used in the pH study due to its poor performance in capturing
glyphosate. To determine the effect of pH on glyphosate adsorption,
the initial pH of 5 ppm glyphosate solution was maintained (pH: 7.7,
control) and adjusted to 4.2, 8.1 and 11.6 respectively, by adding
0.1 mol/L hydrochloric acid or 0.1 mol/L sodium hydroxide to the
glyphosate solution after the addition of SP-PDMAEMA. To deter-
mine the effect of varying initial glyphosate concentrations, the
stock solution was diluted with deionized water to obtain solutions
with glyphosate concentrations ranging from 10 ppm to500 ppb
(10, 7.5, 5, 2.5 and 1 ppm and 500 ppb). Two adsorption-isotherm
models were selected to aid in describing the adsorption equilib-
rium for the adsorbents (Langmuir and Freundlich isotherms).
After the glyphosate adsorption, the complexes of glyphosate
and SP-PDMAEMA and glyphosate and PAMAM6 were filtered us-
ing PS20 filters (polysulfone membrane with 20 kDa molecular
weight cut-off, Sepro Membranes Inc.) under a pressure of 25 psi
while the complexes of glyphosate and activated carbon were
filtered using Acrodisc® 25 mm syringe filters with 1 mm PTFE
membranes (Pall Laboratories) attached to 12 ml plastic syringes.
These filters were used as tests on the filtrates obtained from pure
deionized water passing through these filters did not show any
 L. Samuel et al. / Chemosphere 169 (2017) 437e442 439

Fig. 1. Comparative look at the amine functionalized star polymer and PAMAM dendrimer. (a) Schematic drawing and chemical structure of the amine-functionalized star polymer:
grey region: crosslinked polystyrene (PS) core with PS linear arms (Mw of PS ¼ 4 kDa), blue region: polydimethylaminoethyl methacrylate arms (PDMAEMA, Mw ¼ 7 kDa), Average
arm numbers ¼ 37, green circles: amine group (approximately 45 amine moieties on each arm giving a total of 1665 amine groups per starpolymer) (b) Schematic drawing of the
PAMAM, generation 6 dendrimer, green circles amine functional groups on the terminal ends (about 256 amine groups).

leaching or capture of phosphorous. Glyphosate concentration in

the filtrate was determined by measuring total phosphorous con-
tent with inductively coupled plasma spectrometer (Thermo Sci-
entific ICAP 6300 Duo View Spectrometer), which has a detection
limit of 2 ppb for phosphorous in deionized water. The molecular
formula of glyphosate is C3H8NO5P and there is a theoretical linear
relationship between total phosphorous and glyphosate. The con-
centration of glyphosate in filtrate was finally obtained from the
calibration curve, which is generated by measuring phosphorous
contents in 15 different glyphosate solutions with known concen-
trations (10 ppme500 ppb), in the same deionized water matrix.
Once the glyphosate concentration was determined for each sam-
ple for a given initial concentration tested and the average con-
centration was then determined. Variation in the sample
glyphosate concentrations for each initial concentration was below
±10%. Additionally, ICP analysis of blank deionized water samples
revealed detection of no phosphorous.
Fig. 2. Glyphosate adsorption kinetics relative to 5 ppm feed concnetration onto
activated carbon (blue), star polymer (red) and PAMAM dendrimers (green).
3. Results and discussion

3.1. Effect of adsorbent size and density of amine functional
moieties
The performance of various adsorbents in capturing glyphosate
is shown in Fig. 2. Under the given testing conditions, the efficiency
of SP-PDMAEMA for glyphosate removal is approximately three
times higher than that of activated carbon and eighteen times
higher than that of PAMAM6. For SP-PDMAEMA and PAMAM6,
adsorption equilibrium was achieved after 10 min of contact with
glyphosate, while 20 min of contact was need to achieve adsorption
equilibrium with the activated carbon. This indicates that SP-
PDMAEMA has both a faster removal rate and higher removal ca-
pacity than the other adsorbents tested.
Under neutral conditions, while both SP-PDMAEMA and acti-
vated carbon particles possess large diameters compared to
PAMAM6 dendrimer, (28.05 ± 0.38 nm and 149 mm, respectively)
and hence larger surface areas, they have opposite surface charges.
For SP-PDMAEMA, under neutral conditions a large number of the
amine groups on its arms are positively charged (zeta potential,
z ¼ þ24.6 mV), while activated carbon has a negative zeta-potential
(z ¼ 20.0 mV). Also, under neutral conditions both the first
phosphoric acid (pKa e 0.8) and the carboxylic acid (pKa e 2.3)
protons of glyphosate are fully dissociated giving the glyphosate
molecules a negative surface charge. The negative surface charge
on the activated carbon causes relatively low adsorption via
repulsion of negative groups on the glyphosate, while the positive
surface charge on the star polymer encourages ionic interaction
between the positively charged amine groups and the negatively
charged carboxylic and phosphoric groups on the glyphosate.
Both PAMAM6 and the SP-PDMAEMA have amine functional
groups. However, PAMAM6 dendrimers are approximately 5 times
smaller in diameter (6.0 nm) and only possess 256 amine functional
groups on their terminal surface with relatively lower zeta poten-
tial (z ¼ þ 14.0 mV), whereas each SP-PDMAEMA star polymer has
more than 1500 amine functional groups (about 45 amines per
each hydrophilic arms) with a higher positive potential
(z ¼ þ24.6 mV). The amine groups attached to more than 35-
hydrophilic arms of star polymers could also generate inner
porous environment with higher local density of amines, which
might be advantageous for an efficient glyphosate binding. From
440 L. Samuel et al. / Chemosphere 169 (2017) 437e442

these results, not only the presence of amine groups but also the 3.3. Effect of pH
number, density and arrangement of these functional groups on
polymeric particles seem to be critical in determining its glypho- While the adsorption efficiency of SP-PDMAEMA varies with
sate adsorption efficiency. solution pH, its glyphosate removal efficiency does not fall below
50% except under very basic conditions (pH  11), Fig. 4. With
glyphosate's remaining pKa values ranging from 6.0 to 11
3.2. NMR study
(pKa3 ¼ 6.0 by 2nd phosphoric, and pKa4 ¼ 11 by secondary
amine), it follows that as pH decreases (pH < 7e8) the net negative
H-NMR studies conducted using chloroform (CDCl3) as a solvent
charge of the glyphosate also decreases, reducing the strength of
and butylamine as a proxy for the amine functional groups on both
ionic interactions between the glyphosate molecules and SP-
these polymeric particles, illustrated the mechanism by which the
PDMAEMA, lowering the adsorption efficiency. At higher pH
adsorption process occurs as well as the importance of amine-
(>10), glyphosate has a trivalent negative charge, however the
density on the adsorption process (Fig. 3). Under these condi-
protonation tendency of the amine groups on the star polymer
tions, when the amine groups and the glyphosate concentrations
significantly decreases, losing their positive charge, as the pKa of
are present in 1:1 M ratio, there is competition between carboxylic
protonated amines are around 10 (Homola and James, 1977).
and phosphoric acid moieties to protonate the amine group
(Fig. 3(b)). However, when the amine groups are present in a larger
concentration than glyphosate (in this case a 2:1 M ratio, Fig. 3(c)),
both the carboxylic and phosphoric acid moieties are deprotonated,
implying interaction between each glyphosate molecule and two
amine groups.
Although acid dissociation behavior and amine's protonation
tendency in the NMR solvent (chloroform) are somewhat different
from those in water media as the acidic groups in glyphosate would
be immediately deprotonated in water even without any base
(pKa1 ¼ 0.8 by 1st phosphoric, and pKa2 ¼ 2.3 by carboxylate), the
NMR data still supports the origin of ionic interactions between
glyphosate and an amine-compound depending on their relative
concentrations. The numerous amine groups on the structure of SP-
PDMAEMA provide a local environment within which the amine
molar concentration is more than 2 times larger than that of
glyphosate. Therefore, the ionic interactions between SP-
PDMAEMA and glyphosate follow that seen in Fig. 3(b) and lead
to more complete capture of glyphosate particles (one glyphosate
molecule binds with two amine groups). Fig. 4. Glyphosate adsorption as a function of pH, relative to 5 ppm feed concentration
onto SP-PDMAEMA after 10 min contact time.

Fig. 3. H-NMR spectra of glyphosate mixed with butylamine (serving as a proxy for the amine functional arms of the star polymer) with two different molar ratios under CDCl3. (a)
glyphosate only, (b) 1:1 M ratio of glyphosate and butylamine and (c) 1:2 M ratio of glyphosate and butylamine.
 L. Samuel et al. / Chemosphere 169 (2017) 437e442
Table 1
Kinetic adsorption study of glyphosate remval by star polymer (SP-PDMAEMA) and activaed carbon. Feed concnetration (Co) 5 ppm, qe test e the amount of glyphosate
adsorbed at equilibrium during experiment, k1 e the first order adsorption constant, k2 e second order adsorption constant, qe1 - the amount of glyphosate adsorbed at
equilibrium following 1st order adsorption kinetics, qe2 - the amount of glyphosate adsorbed at equilibrium following 2nd order adsorption kinetics and R (Solomon and
Thompson, 2003) e correlation coefficient.
Adsorbent C0 (ppm) qe test (mg/g) First order kinetics
1
k1 (min ) qe1 (mg/g)
SP-PDMAEMA 5 9.6 0.130
Activated Carbon 5 3.2 0.015
Therefore, there is less possible electrostatic interaction between
glyphosate and SP-PDMAEMA and so adsorption efficiency declines
even further. It should be expected that dramatic reduction in SP-
PDMAEMA adsorption efficiency should be noticeable around pH
9, therefore to maintain its high performance it should only be used
under slightly acidic to neutral conditions.
3.4. Sorption isotherms
Due to the low adsorption efficiency of PAMAM6, adsorption
kinetics and Langmuir and Freundlich isotherms were only fitted to
data from SP-PDMAEMA and activated carbon. Table 1 shows that
the adsorption of glyphosate onto SP-PDMAEMA and activated
carbon is well described by pseudo-second order adsorption ki-
netics (special boundary solution to Langmuir isotherm), similar to
the well-documented results of adsorption studies conducted to
€ tational studies to clarify the SP-PDMAEMA's geometric structure
capture phosphorous (Ozacar, 2003). Further examination of
glyphosate adsorption using the Langmuir and Freundlich
adsorption isotherm models, illustrate that for both adsorbents,
adsorption of glyphosate more closely follows the Langmuir
isotherm with maximum glyphosate adsorption capacity of
229.017 mg/g for SP-PDMAEMA, approximately four times the
maximum adsorption capacity of activated carbon (58.4 mg/g)
tested in this study. Comparison of SP-PDMAEMA's performance to
that of previously examined, functionalized activated carbons such
as KOH-impregnated activated carbon (AC-KOH, Salman et al.,
2012) and the one coated with manganese dioxide (AC-MnO2, Cui
et al., 2012), SP-PDMAEMA has approximately two times and
almost the maximum adsorption capacity of the functionalized
activated carbons (104.2 mg/g for AC-KOH and 283 mg/g for AC-
MnO2, respectively). Further comparison of glyphosate adsorption
by these activated carbons and SP-PDMAEMA, show that the
adsorption efficiency of SP-PDMAEMA follows that seen for AC-
KOH, with pH having the greatest impact under very basic condi-
tions. However, the adsorption efficiency of AC-MnO2 did exhibit a
dependence on pH with optimal adsorption occurring at a pH of 3,
where as for SP-PDMAEMA there is a slight decrease in adsorption
efficiency at low pH. Given the effectiveness of the SP-PDMAEMA in
removing glyphosate, it should be expected that SP-PDMAEMA
would efficiently remove other organophosphorous pesticides
(ex. glufosinate) would through acid-base interactions.
4. Conclusion
Given glyphosate's widespread use, its presence in the envi-
ronment and the health concerns associated with its ingestion, it is
important to find an effective method for its removal from water
and aqueous solutions. Glyphosate is also a good model compound
representing organophosphate/phosphoric acid-base herbicides to
demonstrate the concept that uniquely designed amine-
functionalized star polymer can be used to effectively facilitate
their capture. Among all of the adsorbents examined in this study,
the tailored star polymer (SP-PDMAEMA) comprised of more than
441
Second order kinetics
2
R k2 (g/mg/min) qe2 (mg/g) R2
1.50 0.9437 0.086 9.63 0.9994
1.04 0.9263 0.042 3.18 0.9932
35-linear polymer chains, each containing a plurality of pendent
amines, outperformed both the tested activated carbon and
PAMAM6, which has low amine group density on its surface. The
high adsorption efficiency of the SP-PDMAEMA within the rela-
tively short contact time of 10 min makes the material a potential
adsorbent for use in a scalable process requiring fast and effective
removal of glyphosate and possibly other organophosphorous
compounds. Moreover, since the functional group of the star
polymers can be tailored depending on a target compound, this
could be a basic material platform to deal with a challenging im-
purity in water by coupling with activated carbon and/or other
conventional water treatment methods. Hence, we demonstrated
glyphosate-removal efficacy using a simplified aqueous media
formulated with DI water without using real drinking and/or sur-
face water. Future work to improve our understanding of SP-
PDMAEMA's glyphosate adsorption efficiency will include compu-
and its complexation behavior with glyphosate in water.
Acknowledgements
The authors thank Dr. Reinhold Dauskardt and Stanford Uni-
versity's Environmental Measurement Facility for their assistance
in conducting ICP analysis on the samples for this work.
References
Assalin, M.R., De Moraes, S.G., Queiroz, S.C., Ferracini, V.L., Duran, N., 2009. Studies
on degradation of glyphosate by several oxidative chemical processes: ozona-
tion, photolysis and heterogeneous photocatalysis. J. Environ. Sci. Health, Part B
45 (1), 89e94. http://dx.doi.org/10.1080/03601230903404598.
Bozkaya-Schrotter, B., Daines, C., Lescourret, A.S., Bignon, A., Breant, P.,
Schrotter, J.C., 2008. Treatment of trace organics in membrane concentrates I:
pesticide elimination. Water Sci. Technol. 8 (2), 223e230. http://dx.doi.org/
10.2166/ws.2008.056.
Buffin, D., Jewell, T., 2014. Health and Environmental Impacts of Glyphosate: The
Implications of Increased Use of Glyphosate in Association with Genetically
Modified Crops. Friends of the Earth. http://www.foe.co.uk/resource/reports/
impacts_glyphosate.pdf (accessed 07.16.14).
Cui, H., Li, Q., Qian, Y., Zhang, Q., Zhai, J., 2012. Preparation and adsorption perfor-
mance of MnO2/PAC composite towards aqueous glyphosate. Environ. Technol.
33 (17), pp.2049e2056.
European Union, 1991. EU Council Directive 90/414/EEC. European Commission,
Brussels.
Freuze, I., Jadas-Hecart, A., Royer, A., Communal, P.Y., 2007. Influence of complex-
ation phenomena with multivalent cations on the analysis of glyphosate and
aminomethyl phosphonic acid in water. J. Chromatogr. A 1175 (2), 197e206.
http://dx.doi.org/10.1016/j.chroma.2007.10.092.
Fritschi, L., McLaughlin, J., Sergi, C.M., Calaf, G.M., Le Curieux, F., Forastiere, F.,
Kromhout, H., Egeghy, P., Jahnke, G.D., Jameson, C.W., Martin, M.T., 2014. Car-
cinogenicity of tetrachlorvinphos, parathion, malathion, diazinon, and glypho-
sate. Lancet Oncol. http://dx.doi.org/10.1016/S1470-2045(15)70134-8.
Gasnier, C., Dumont, C., Benachour, N., Clair, E., Chagnon, M.C., Se ralini, G.E., 2009.
Glyphosate-based herbicides are toxic and endocrine disruptors in human cell
lines. Toxicology 262 (3), 184e191. http://dx.doi.org/10.1016/j.tox.2009.06.006.
Groundwater and Drinking Water Consumer Factsheet on: GLYPHOSATE, 2015. U.S.
Environmental Protection Agency, Washington, D.C. https://safewater.zendesk.
com/hc/en-us/articles/212076457-4-What-are-EPA-s-drinking-water-regula-
tions-for-glyphosate- (accessed on 08.12.15).
Guo, Z.X., Cai, Q., Yang, Z., 2005. Determination of glyphosate and phosphate in
water by ion chromatographydinductively coupled plasma mass spectrometry
detection. J. Chromatogr. A 1100, 160e167. http://dx.doi.org/10.1016/
442 L. Samuel et al. / Chemosphere 169 (2017) 437e442
j.chroma.2005.09.034.
Hamerlinck, Y., Mertens, D.H., Vansant, E.F., 1994. Activated Carbon Principles in
Separation Technology. Elsevier, New York.
Ho, M.W., Cherry, B., 2009. Death by multiple poisoning, glyphosate and Roundup.
Sci. Soc. 42, 14.
Homola, A., James, R.O., 1977. Preparation and characterization of amphoteric
polystyrene lattices. J. Colloid Interface Sci. 59 (1), 123e134. http://dx.doi.org/
10.1016/0021-9797(77)90346-0.
Hu, Y.S., Zhao, Y.Q., Sorohan, B., 2011. Removal of glyphosate from aqueous envi-
ronment by adsorption using water industrial residual. Desalination 271 (1),
150e156. http://dx.doi.org/10.1016/j.desal.2010.12.014.
Jayasumana, C., Gunatilake, S., Senanayake, P., 2014. Glyphosate, hard water and
nephrotoxic metals: are they the culprits behind the epidemic of chronic kidney
disease of unknown etiology in Sri Lanka? Int. J. Environ. Res. Public Health 11
(2), 2125e2147.
Lee, V.Y., Havenstrite, K., Tjio, M., McNeil, M., Blau, H.M., Miller, R.D., Sly, J., 2011.
Nanogel star polymer architectures: a nanoparticle platform for modular pro-
grammable macromolecular self-assembly, intercellular transport, and dual-
mode cargo delivery. Adv. Mat. 23 (39), 4509e4515 doi:10.1002/
adma.201102371 or 10.1002/adma.201190158.
Mishra, M., Kobayashi, S., 1999. Star and Hyperbranched Polymers, vol. 53. CRC
Press, New York, pp. 201e239.
Mohan, D., Pittman, C.U., 2006. Activated carbons and low cost adsorbents for
remediation of tri-and hexavalent chromium from water. J. Hazard. Mater 137
(2), 762e811.
€
Ozacar, M., 2003. Equilibrium and kinetic modelling of adsorption of phosphorus on
calcined alunite. Adsorption 9 (2), 125e132. http://dx.doi.org/10.1023/A:
1024289209583.
Paganelli, A., Gnazzo, V., Acosta, H., Lo pez, S.L., Carrasco, A.E., 2010. Glyphosate-
based herbicides produce teratogenic effects on vertebrates by impairing reti-
noic acid signaling. Chem. Res. Toxicol. 23 (10), 1586e1595. http://dx.doi.org/
10.1021/tx1001749.
Qian, K., Tang, T., Shi, T., Li, P., Li, J., Cao, Y., 2009. Solid-phase extraction and residue
determination of glyphosate in apple by ion-pairing reverse-phase liquid
chromatography with pre-column derivatization. J. Sep. Sci. 32 (14),
2394e2400. http://dx.doi.org/10.1002/jssc.200900118.
Relyea, R.A., 2005. The lethal impact of Roundup on aquatic and terrestrial am-
phibians. Ecol. Appl. 15 (4), 1118e1124. http://dx.doi.org/10.1890/04-1291.
Richard, S., Moslemi, S., Sipahutar, H., Benachour, N., Seralini, G.E., 2005. Differential
effects of glyphosate and roundup on human placental cells and aromatase.
Environ. Health Perspect. 716e720. http://dx.doi.org/10.1289/ehp.7728.
Salman, J.M., Abid, F.M., Muhammed, A.A., 2012. Batch study for pesticide glypho-
sate adsorption onto palm oil fronds activated carbon. Asian J. Chem. 24 (12),
5646.
Scho€nbrunn, E., Eschenburg, S., Shuttleworth, W.A., Schloss, J.V., Amrhein, N.,
Evans, J.N., Kabsch, W., 2001. Interaction of the herbicide glyphosate with its
target enzyme 5-enolpyruvylshikimate 3-phosphate synthase in atomic detail.
Proc. Natl. Acad. Sci. 98 (4), 1376e1380. http://dx.doi.org/10.1073/
pnas.98.4.1376.
Solomon, K., Thompson, D., 2003. Ecological risk assessment for aquatic organisms
from over-water uses of glyphosate. J. Toxicol. Environ. Health, Part B 6 (3),
289e324.
Speth, T.F., 1993. Glyphosate removal from drinking water. J. Environ. Eng. 119 (6),
1139e1157. http://dx.doi.org/10.1061/(ASCE)0733-9372(1993)119:6(1139).
Stalikas, C.D., Konidari, C.N., 2001. Analytical methods to determine phosphonic and
amino acid group-containing pesticides. J. Chromatogr. A 907 (1), 1e19. http://
dx.doi.org/10.1016/S0021-9673(00)01009-8.