Cleaner Engineering and Technology 5 (2021) 100339

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Cleaner Engineering and Technology

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Incorporation of biogenic zinc nanoparticles into a polymeric membrane:

Impact on the capture of organic herbicides
Salma Shad a, b, Nadia Bashir a, Marie-France Belinga-Desaunay Nault b, Iseult Lynch b, *
a
Department of Chemistry, Hazara University, Mansehra, Pakistan
b
School of Geography, Earth and Environmental Sciences, University of Birmingham, United Kingdom

A R T I C L E I N F O A B S T R A C T

Keywords: Nanoparticle incorporated membranes are potential tools to remove hazardous organic pollutants from drinking
Adsorption water sources. Cellulose acetate membranes were impregnated by incorporating zinc nanoparticles, produced
Topography using a green synthesis with Mentha plant extract utilizing microwave energy. The synthesized nanoparticles
Cellulose acetate
were extensively characterized using ultraviolet–visible spectroscopy, X-ray diffraction, Scanning electron mi­
Metolachlor
Acetochlor
croscopy, energy dispersive X-ray spectroscopy and Nanoparticle tracking analysis. The spectroscopy results
showed an absorbance peak at 300 nm, confirming the successful synthesis, while X-ray diffraction confirmed
that the particles are crystalline with a mean particle size of 36 nm. The surface roughness and topography of the
zinc nanoparticle impregnated membranes was studied using atomic force microscopy to check the homogeneity
of dispersion of the nanoparticles in the membrane. The efficiency of the zinc nanoparticles and the zinc
nanoparticle loaded cellulose acetate membranes for adsorption of organic herbicides such as metolachlor and
acetochlor was studied. The particles themselves and the particle-embedded membranes proved to be very
adsorbent due to their unique structural properties, providing large surface area and high adsorption capacity.
The incorporation of zinc nanoparticles into the membrane decreased the time needed for the removal of the
selected herbicides relative to that of the nanoparticles alone, and provides a promising method for water
purification.

1. Introduction types of herbicides or weedicides, 30 types of fungicides, 5 types of

acaricides, 6 types of rodenticides, and 108 insecticides are currently
Increasing population, urbanization and economic development are used in Pakistan, according to the environmental assessment and water
collectively leading to increasingly frequent occurrences of pollution quality monitoring program of the Punjab Private Sector Groundwater
and contamination of water, which have impacted not just aquatic Development Project (PPSGDP, 2002), and reviewed by Mehmood et al.
ecosystems but the whole environment (Yao et al., 2015). The most (2017). Herbicides such as Acetochlor [2-chloro-N-(ethoxymethyl)-N-
common synthetic pollutants entering surface or ground water include (2-ethyl-6-methylphenyl) acetamide] and metolachlor [2-chloro-N
plastics (Guzzetti et al., 2018), pesticides (Burgos-Aceves et al., 2018), -(2-ethyl-6-methylphenyl)-N-(1-methoxypropane-2yl) acetamide) are
pharmaceuticals (Hodkovicova et al., 2019), pesticides (Jiang et al., widely used due to their effectiveness as both pre- and post- (crop)
2015), as well as persistent organic pollutants (Mehmood et al., 2017). emergence herbicides to broaden the spectrum of weed control on va­
Among these, freshwater contamination by pesticides has caused the riety of crops. Acetochlor (C14H20ClNO2) and metolachlor
highest public concern about the quality of drinking water. This has led (C15H22ClNO2) belong to the group of chloroacetanilide herbicides, and
to renewed pesticide monitoring, research and the call for stricter water are inception herbicides used against broad leaf, grassy and barnyard
quality standards and more robust enforcement of existing standards weeds, digitaria grass, panic dichotomique and foxtails (diaspore).
(Köck-Schulmeyer et al., 2014). These herbicides are sprayed on soybean, corn, peanut vine, sorghum
Pakistan ranks second among South Asian countries in terms of vulgare, potatoes, cotton, safflower, and for control of annual grasses
overall consumption of pesticides, on account of its largely agricultural and small seeded broadleaf weeds in more than 70 agricultural crops
economy and growing population (Waheed et al., 2017). More than 39 worldwide (Zemolin, 2014). Several important vegetable crops in

* Corresponding author.
E-mail address: [email protected] (I. Lynch).

https://doi.org/10.1016/j.clet.2021.100339
Received 12 April 2021; Received in revised form 22 October 2021; Accepted 4 November 2021
Available online 6 November 2021
2666-7908/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
S. Shad et al. Cleaner Engineering and Technology 5 (2021) 100339

Pakistan, such as carrots, are heavily affected by weeds, driving wide­ (Fe, − 0.44 E0/V) (Bratsch, 1989). The rate of contaminant degradation
spread utilization of herbicides such as Dual Gold® whose active by ZnNPs might be faster than that of nZVI, while Zn NPs are considered
ingredient is S-metolachlor (Amjad et al., 2013). Sugar cane, considered an effective adsorbing agent for pesticides (Bokare et al., 2013).
a cash crop in Pakistan, is also greatly affected by the presence of weeds, In the present study, a green synthesis method (using both low en­
and acetochlor is widely used (often in combination with atrazine) to ergy and plant extract as reducing agent) was used for the synthesis of
tackle the major weed C. stricta (Hussain et al., 2020). zero valent Zn NPs which were then characterized and used for the
Both acetochlor and metolachlor are defined as leachers and con­ adsorption/removal of acetochlor and metolachlor, as representative
taminants under the classification of pesticides in terms of their poten­ herbicides, from aqueous solution. After considering the advantages of
tial for ground water contamination. Due to their high water solubility the ZnNPs to remove herbicides from aqueous medium, the utility of the
(233 mgL− 1 for acetochlor and 488 mgL− 1 for metolachlor – see ZnNPs was further improved by integrating them into cellulose acetate
Table S1), and moderate to long persistence in soil and water bodies, (CA) membranes to reduce the potential risks associated with NP release
these active compounds are frequently found in both European and into the environment. CA is produced from processed wood pulp and as
Asian freshwaters (PPDB, 2020). Acetochlor and metolachlor are both such is a renewable resource and is biodegradable. The synthesized NPs
endocrine disrupting chemicals and potential human carcinogens, were embedded in the polymeric CA membrane and analyzed by atomic
which can induce oxidative stress, and immune toxicity in non-target force microscope (AFM) prior to additional adsorption studies to assess
organisms (Jiang et al., 2015). The European Union (EU) has estab­ their efficiency for the removal of the herbicides.
lished maximum residue limits for both herbicides in different food
products, varying from 0.02 to 0.05 mg kg− 1 (EU, 2020). Chlor­ 2. Materials and methods
oacetanilide herbicides are considered to be detoxified in biological
systems due to the formation of glutathione-acetanilide conjugates, 2.1. Materials and instruments
which is mediated by glutathione–S-transferase present in plants,
mammals and microorganisms (Field and Thurman, 1996). Organic and Standards of two organic herbicides, Metolachlor and Acetochlor
inorganic sulfides react through nucleophilic attack on the 2-chloro (Fig. S1) were purchased from Acros organic chemicals (Lahore,
group of acetanilide herbicides (Stamper and Tuovinen, 1998). Resi­ Pakistan). Cellulose acetate and zinc nitrate [Zn(NO3)2] were purchased
dues of acetochlor and metolachlor constitute a significant source of from Merck (KGaA, Darmstadt, Germany) and utilized without further
ecological (air, water and soil) contamination, representing a contin­ purification.
uous threat to the co-existence of plant and animal ecosystems. A UV/Visible (UV/Vis) double beam spectrophotometer (Lambda 25,
Currently, total pesticide consumption globally is 2.5 Mt, of which more PerkinElmer, Shelton, CT, USA) was used to confirm the formation of the
than 40% are herbicides (Fenner et al., 2013). Application of pesticides zero valent Zn NPs. NPs were produced using a domestic microwave
is notoriously imprecise: just a small percentage (0.1%) goes to the oven {INPUT: 230–240V–50Hz 1200W (MICRO), OUTPUT: 700W 2450
target area while 99.7% leeches into the environment (soil, surface and MHz}.
ground water) posing a threat to living organisms (Pimentel, 1995). It is
vitally important to develop efficient and stable materials to remove 2.2. Quantification of standard solutions of herbicides
pesticides and other contaminants from water to meet the ongoing
challenge of providing fresh and clean water in satisfactory amounts. For Herbicide (acetochlor & metolachlor) solutions were prepared for
this purpose, new treatment methods are needed that must be cheap, quantification via a standard curve, by dissolving 1 mL of herbicide in
renewable, non-polluting themselves, and more efficacious as compared 100 mL of deionized water and quantifying by UV/Vis spectrophotom­
to the current remediation techniques. eter and the maximum absorption wavelengths for metolachlor and
Nanotechnology is emerging as an effective technology to solve acetochlor were determined to be 320 nm and 423 nm, as shown in
water quality problems (Bottero et al., 2006), with nanomaterials (Lu Fig. S2. The maximum absorbances were used to confirm the amount of
et al., 2016) and nanostructured surfaces (Obare and Meyer, 2004) adsorbate on the adsorbent surface.
contributing to the development of more effective treatment procedures.
Nanomaterials (NMs) have strong adsorption capacities and reactivity 2.3. Preparation of ZnNPs nanoparticles using Mentha Piperita (Mentha)
due to their small size, high specific surface area and high mobility in leaf extract
solution (Khin et al., 2012). Zero-valent metal nanoparticles (ZVM NPs),
metal oxide NPs, carbon nanotubes, and recently graphene membranes Extract of the Mentha plant was used for the synthesis of ZnNPs, due
and nano-composites, are the most broadly studied NMs for environ­ to their medicinal value and ease of availability. Fresh and healthy
mental remediation (Xue et al., 2016). NMs have been reported to suc­ leaves of Mentha were collected from the botanical garden of Hazara
cessfully remove heavy metals (Tang et al., 2014), organic pollutants University, Mansehra and washed with tap water followed by distilled
(Yan et al., 2015), inorganic anions (Liu et al., 2014)), and bacteria water. Leaves were dried in the dark at room temperature and cut into
(Kalhapure et al., 2015) from contaminated water, and NMs thus show small pieces. The leaves (5 g) were placed in a flask containing 100 mL of
great promise for applications in water and wastewater treatment. Most distilled water and heated for 3 min in a domestic microwave oven at
studies on contaminant degradation in water and wastewater treatment medium low power. A raw extract of yellowish color was obtained and
by the reductive ZVM NPs have been performed using nanoscale iron filtered twice through Whatman filter paper (diameter: 12.5 cm) to
particles (nZVI) to date, such as the use of nZVI particles for remediation remove all solid material present in the extract. The filtrate was refrig­
of alachlor and atrazine from contaminated water (Bezbaruah et al., erated at 4 ◦ C until further use.
2009), and there are numerous approaches for synthesis of nZVI parti­ 10 mM Zn (NO3)2 solution was prepared by adding 0.279 g of pre­
cles for use in water treatment (Lu et al., 2016). Zero valent zinc cursor salt in a 1000 mL volumetric flask and diluted with deionized
nanoparticles (ZnNPs) are increasingly being considered as a potential water. The solution of precursor salt and Mentha extract was mixed in
alternative; for example Bokare et al. (2013) assessed the kinetics of the ratio 1:9 and heated at 48◦ for 2 min in the microwave oven (me­
dechlorination of octachlorodibenzo-p-dioxin by nZVZ (Bokare et al., dium-low power mode). The synthesized precipitates were centrifuged
2013), while Shad et al. (2020) assessed the efficiency of microwave and washed repeatedly with deionized water. The pellet was dried and
synthesized nZVZ particles for removal of dissolved agricultural con­ studied by UV–Visible spectrophotometry.
taminants (phosphate, ammonia, nitrate, lead and chloride) from canal
water (Shad et al., 2020). Having a negative standard reduction poten­
tial (− 0.762 E0/V), Zn becomes a stronger reductant as compared to iron

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S. Shad et al. Cleaner Engineering and Technology 5 (2021) 100339

2.4. Membrane preparation and incorporation of ZnNPs in the membrane curves (y = ax + b), the total amount of adsorbed contaminant per g of
adsorbent was calculated as the difference between the initial and final
The synthesized ZnNPs were incorporated into cellulose acetate (CA) concentrations at equilibrium, using the equations:
which provides support for the NPs. The membranes were prepared
C0 − Ce
using the procedure reported earlier (Wu et al., 2005). Briefly, 5 g of CA %adsorption = × 100 (1)
co
was dissolved in 50 mL of acetone and stirred continuously, until the
complete dissolution of the polymer. About 0.1 mg of ZnNPs was added (C0 − Ce )
to the solution and homogenized by continuous stirring. The prepared qe = V (2)
W
solution was cast onto a dry glass Petri dish (200 mm in diameter) where
the phase conversion took place. The film took 2 min to dry and was where, C0 represents the initial concentration of the selected herbicide
used as prepared for further study. A blank membrane without the (mgL− 1), Ce is the aqueous phase concentration at equilibrium (mgL− 1),
incorporation of ZnNPs was prepared as a control. qe is the amount adsorbed at equilibrium (mg/g adsorbent− 1) by both
NPs and the NPs incorporated membrane, whereas V is the total volume
2.5. Characterization techniques (L) and W is the weight of adsorbent (g).

Biosynthesized ZnNPs were characterized by UV/Vis (concentra­ 3. Results and discussion

tion), X-ray diffraction (XRD), Scanning electron microscopy (SEM),
Energy dispersive X-ray analysis (EDX), nanoparticle tracking analysis 3.1. UV/Vis analysis of synthesized ZnNPs
(NTA) and when embedded in the cellulose acetate membrane by atomic
force microscopy (AFM). UV–visible spectrophotometry is commonly used to confirm the
XRD analysis of the NPs was performed using an X-ray diffractometer synthesis of NPs. Previous published literature confirmed that the ab­
(Analytical X pert Pro) with an X-ray generation source, at the School of sorption spectrum of ZnNPs lies in the range of 350–380 nm (Lu et al.,
Chemistry, University of Birmingham, UK, and the diffraction data was 2016). The zero valent metallic ZnNPs gave the highest peak at 300-350
noted in the 2Ɵ range of 20–70◦ at tube voltage as per previous reports nm which confirmed the formation of ZnNPs, as shown in Fig. S5 in the
(Jamdagni et al., 2018). A PHILIPS XL 30 Environmental Scanning supplementary information.
Electron Microscope with a field emission gun (ESEM FEG) coupled with
Energy-dispersive X-ray spectroscopy (EDX) was used for analysis and 3.2. Characterization of synthesized ZnNPs
mapping of the sample. EDX at 20 KeV was used to study the elemental
composition, % of every element and purity of the ZnNPs. Nanoparticle 3.2.1. XRD analysis of the ZnNPs
tracking analysis (NTA) using Nanosight LM-20 was used to measure the XRD was used to identify the phase structure and purity of the
dispersion characteristics, i.e., size and size distribution of the ZnNPs in ZnNPs. XRD analysis gave the actual diameter of ZnNPs as 36.01 nm.
Milli Q water as the medium. An XE-100 Atomic scanning probe Mi­ Based on the XRD pattern, the synthesized NPs have high purity and a
croscope, at University of Birmingham, UK was used for atomic force crystalline structure as the diffraction peak is narrow and intense. The
microscopy (AFM) analysis of the ZnNPs. The NP-fabricated membrane result was compared with the standard XRD pattern (JCPDS 36–451) for
was also analyzed by AFM to study the surface roughness and topog­ confirmation. The XRD pattern shows prominent diffraction peaks
raphy of the membrane. indexed with the cubic closed pack (CCP) structure of ZnNPs, as shown
in Fig. 1(a). The distinct diffraction peaks at 31.70◦ , 34.36◦ , 36.22◦ ,
2.6. Adsorption of selected herbicides to the ZnNPs 47.54◦ , 56.54◦ , 62.79◦ , 66.25◦ , 67.86◦ , 69.03◦ , 72.60◦ and 76.76◦
correspond to a cubic closed pack structure. The size of the ZnNPs was
The efficiency of the ZnNPs and ZnNPs-CA membrane were assessed calculated using the Debye Scherer’s formula and the pattern was
to compare the % removal of herbicides from the aqueous solution. For recorded in 2θ geometry in the range 36–50 nm, showing all the
this study, a low concentration (0.1 mg) of ZnNPs was immersed in 100 prominent Bragg reflections in a good agreement with the peak positions
mL of 0.5 g/L herbicide solutions. For each aliquot, the UV/Vis spectrum published for ZnO NPs (Das et al., 2013). The XRD pattern confirms the
was taken to study the maximum absorbance. Aliquots of the solution absence of impurities in the biosynthesized ZnNPs.
were taken regularly over time (2 min) and the herbicide concentration
was determined by UV-VIS spectroscopy using the calibration curve 3.2.2. SEM coupled with EDX analysis of ZnNPs
(0.1–1 g/L) of the herbicides (Fig. S3) to convert absorbance to con­ The size, growth and surface morphology of the NPs were studied by
centration. Initially, the effect of different concentrations (0.1–0.4 mg) scanning electron microscopy with EDX analysis of the distinctive
of the ZnNPs on the calibrated (0.5 g/L) solution of each herbicide was atomic structure. The micrographs confirmed that the NPs formed were
assessed to determine the optimal concentration to achieve efficient cubic in shape and that they grow and accumulate to form flower-shaped
removal. bundles, as shown in Fig. 1(b). The particle clustering and agglomera­
All solutions were prepared in triplicate, including blanks prepared tion is due to the polarity and electrostatic attraction between the plant
without the addition of adsorbent (Fig. S4). Adsorption curves were metabolites (Menta extract) and the metal salt (Abdul Salam et al.,
plotted as a function of time, to determine the capacity of the ZnNPs for 2014), and indeed previous literature has shown that using plant ex­
removal of the herbicides. tracts as the reducing agent may lead to primary particle agglomeration
(Agarwal et al., 2017).
2.7. Adsorption of selected herbicide to the ZnNPs-embedded CA The elemental analysis of the Zn NPs is shown in Fig. 1(c) which
membranes exhibits a very small peak of O while the most intense peak for Zn was
recorded at 8.025 keV. Beside these peaks there is no evidence of any
To compare the efficiency of NPs and NPs fabricated membrane, a other element which confirms the purity of the metallic nanoparticles.
small portion (2 cm x 2 cm) of CA membrane and ZnNPs-CA membrane The weight percent of zinc present in the sample is 98.34% while that of
was cut and immersed into the 0.500 g/L solutions of herbicides. Every O is 1.66%. The elemental peaks indicate the reduction of metals ions
2 min, a 1 mL aliquot was pipetted into a UV–vis cuvette and measured into elemental Zn (Fakhari et al., 2019).
by UV/Vis (320 nm and 423 nm for metolachlor and acetochlor,
respectively) to determine the remaining herbicide concentration at 3.2.3. Nanoparticle tracking Analysis (NTA) of the ZnNPs
each time point. Using the equations of the slopes of the calibration The particle size distribution of the ZnNPs is shown in Fig. 1(d). NTA

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Fig. 1. Characterization of the zero valent Zn NPs: (a) XRD analysis of the synthesized Zn NPs. (b) SEM image of the Zn NPs. (c) Elemental composition of the Zn NPs
as determined by EDX analysis. (d) Particle number and size distribution of the Zn NPs by NTA with the inset showing the Brownian motion of the Zn NPs in water.

Fig. 2. AFM images of the Zn NPs showing (a) surface roughness; (b) topography; and (c) the 3D-AFM magnification of the Zn NPs (25× 25 μm).

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indicated 2 distinct peaks at 36 and 79 nm, with a very small additional 3.3. Adsorption of selective herbicides onto the surface of ZnNPs
peak at 117 nm, resulting in a relatively broad size distribution. The
nonparametric distribution shown in Fig. 2(d) indicates that the ma­ Acetochlor and metolachlor (0.5 g/L) were utilized as analytes to
jority of the ZnNPs are around 36 nm in size, with a small proportion of investigate the adsorption of herbicides on the surface of synthesized
particles having larger hydrodynamic diameters, which might be due to ZnNPs (0.1 mg). Fig. 4(a) indicates that the adsorption of both herbi­
the formation of agglomerates from the primary particles in the sus­ cides is a time dependent process; the adsorption mechanism was very
pension (Wagner et al., 2016). quick within the first 10 min and then slowed over longer exposure
times. Fig. 4 (b) indicates the % removal of the herbicides by the ZnNPs
3.2.4. AFM analysis of ZnNPs and ZnNPs dispersed in the CA film and the summary data is given in Table 1.
AFM can be used to determine the size of NPs, and to provide in­ Fig. 4(a) shows that 0.1 mg of the ZnNPs took less than 60 min to
formation regarding the roughness of surfaces including those contain­ remove 97% of the metolachlor herbicide while 61% of the initial
ing NPs, such as the ZnNPs embedded cellulose acetate (CA) films. The concentration of acetochlor was adsorbed onto the surface of the NPs
size of the metallic NPs was studied from tip corrected measurements from the aqueous solution. The concentration of both herbicides was
which confirmed the size of ZnNPs to be in the range of 36–50 nm as measured at regular intervals by UV–Visible spectrophotometry and %
shown in Fig. 2(a&b). The 3D view of the sample at a 25 × 25 μm scan is adsorption was calculated by the expression in (Eq. (1)). The adsorption
shown in Fig. 2(c). mechanism was identified from the adsorption isotherm which explains
The AFM analysis of the ZnNPs showed that changes in the various how the solutes are interacting with the adsorbent. The results indicated
parameters like temperature, time and concentration ratio have a sig­ that the herbicide removal percentage reached the highest values at 60
nificant effect on the shape and size of the NPs. The particles were well min.
dispersed on the surface of the mica sheet, demonstrating a hydrophilic ZnNPs are found most effective against Metolachlor herbicide as
surface coat. compared to acetochlor, due to the higher adsorption of Metolachlor
The synthesized ZnNPs were embedded into a CA membrane to onto the surface of NPs.
prepare a filter for herbicide contaminated water. Fig. 3 (a&b) illustrates
the AFM image of Zn NPs incorporated in CA membrane and it was
observed that NPs were fully dispersed in the membrane as shown in 3.4. Adsorption of selective herbicides by the ZnNPs incorporated
Fig. 3(c). The surface roughness was measured and the small cavity in­ membrane
dicates the pores. The presence of NPs in the membrane matrix created
some superficial disorder on the surface causing increased surface The CA membranes showed good results in the absorptions of
roughness. The vertical profile of the membrane is displayed by the color organic herbicides from the aqueous solution. The time of adsorption
intensity, with the bright regions corresponding to the nanoparticles decreases as compared to that of the ZnNPs alone, as shown in Fig. 4 and
protruding from the surface while the dark regions represent de­ Table 2 which present the results of the % herbicide adsorption of the CA
pressions and pores. The membrane surfaces remained intact during use, membrane embedded with 0.1 mg nanomaterials. The adsorption time
indicating that the integrity of the membrane was well conserved decreased to 20 min for metolachlor and in the case of acetochlor 61% of
following functionalization with the Zn NPs. the total herbicide was removed from the samples within 30 min, as
shown in Fig. 5. It is concluded that membranes fabricated with NPs are
more effective than the NPs alone, as the time taken for adsorption of the
herbicides reduces to just 20 min for 99.8% removal of metolachlor from

Fig. 3. AFM images of ZnNPs CA membrane at different magnifications showing (a) Blank membrane of CA; (b) 3-D Topography image of ZnNPs CA membrane (25
× 25 μm); and (c) 3D-image showing dispersion of ZnNPs in CA membrane (25 × 25 μm).

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Fig. 4. Removal of model pesticides by the Zn NPs. (a) UV–Vis absorption spectra corresponding to the concentrations remaining in solution over time from the
starting concentration of 0.5 g/L herbicide following exposure to 0.1 mg Zn NPs (100 mL) over time; (b) the UV–Vis data replotted as % removal of the herbicides by
0.1 mg/100 mL Zn NPs.

NPs or free Zn2+ to the environment, which may have eco-toxicological

Table 1
consequences since Zn2+ is a known antimicrobial (McDevitt et al.,
Efficiency of ZnNPs for removal of organic herbicides – the initial herbicide
2011) as well as being an essential element (at low concentrations).
concentration was 0.5 g/L and the ZnNPs concentration was 0.1 mg/100 mL
solution, as % of initial solution adsorbed after 60 minutes.
Assessment of the toxicity of ZnO and ZnNPs to the model luminescent
bacteria, Vibrio fischeri, determined that ZnNPs were less toxic than ZnO
Herbicides Nanoparticles Adsorption Time (min) % adsorption
NPs, likely as a result of a lower release of Zn2+ ions from ZnNPs (Zhang
Metolachlor ZnNPs 60 97 ± 0.1 et al., 2020).
Acetochlor ZnNPs 60 61 s ± 0.4
A range of NP chemistries have been assessed for their ability to
perform the complete removal of such herbicides from drinking water,
leading to a consensus that NPs are highly effective for purification of
Table 2 drinking water (Nair and Pradeep, 2007). The relatively high herbicide
Adsorption of selected herbicides (0.5 g/L) by CA membrane alone and ZnNPs adsorption onto the surface of metallic NPs is due to the large number of
modified CA membrane (0.1 mg Zn NPs / 5g CA) determined over 30 min. adsorption sites and the high surface area of (metallic) NPs. A drawback
Herbicides Nanoparticles Adsorption Time (min) % adsorption to their application is the fact that NPs could be lost through rapid
Metolachlor None 30 13 ± 0.04 oxidation and hydrolysis; to address this risk the stability was enhanced
Acetochlor None 30 9 ± 0.1 by fabrication of NPs into a membrane support (Wu et al., 2005). These
Metolachlor ZnNPs 20 99.8 ± 0.03 nano-dimension and energetic surface atoms are believed to help in
Acetochlor ZnNPs 30 61.4 ± 0.1
overcoming the thermochemical and entropic barriers in bringing about
the adsorption and any subsequent degradation reactions (Nair and
water solution by ZnNPs CA membrane. Triplicate samples were pre­ Pradeep, 2007). The adsorption of chlorinated halocarbons using metal
pared and checked to gain the accuracy, with good reproducibility. NPs demonstrates that hydrocarbons and chlorinated compounds un­
Given that the concentrations of herbicides utilized here were dergo catalytic destruction in solution to form carbon, metal and
deliberately high to show the enormous capacity of the ZnNPs for the non-metal halides as byproducts. In the solution phase, herbicides get
selected herbicides, it is clear that the chemistry of the supported ZnNPs adsorbed onto the NPs and upon interaction for long times the NPs
can be utilized for the complete removal of such organochlorine or precipitate with the adsorbed pesticides. In the case of NPs supported
organosulfur pesticides from drinking water. Subsequent work will onto the CA membrane, these were more effective for the complete
confirm the re-usability of the membranes, and confirm that the ZnNPs removal of the herbicides since there was no issue of NP precipitation or
content does not vary significant during use, which would signify loss of agglomeration, and the membranes are more environmentally friendly
since there is less risk of release of NPs into the purified water as they are

Fig. 5. Removal of model pesticides by Zn NPs embedded into CA membranes. (a) UV–Vis absorption spectra corresponding to the concentrations remaining in
solution over time from the starting concentration of 0.5 g/L herbicide following exposure to a 2 cm disc of the ZnNPs-CA membrae (prepared from 0.1 mg Zn NPs
and 5 g of CA) over time; (b) the UV–Vis data replotted as % removal of the herbicides by the ZnNPs-CA membrane composite.

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suitably anchored to inert surfaces, thereby resolving the major draw­ on detection of very low-level contamination such as to meet drinking
back of utilizing NPs in suspension. water standards or environmental quality limits, and as such have
The adsorption isotherms of the ZnNPs-CA membrane system focused on pushing the limits of detection, and indeed many are now
confirmed that 99.8% of metolachlor and 61.4% of acetochlor herbi­ able to detect pesticides such as atrazine at levels down to ng/mL (ppb)
cides were successfully removed by the polymeric membrane embedded levels (Xiang et al., 2020), suggesting that sufficiently accurate mixing
with ZnNPs whereas a decrease in the time taken for adsorption was of recovered pesticides with fresh pesticide formulation could be easily
observed. The enhanced binding of metolachlor compared to acetochlor achieved on site by farmers. Parra et al. summarized several re­
by the Zn NPs can be explained by the differences in water solubility, quirements of physical sensors for precision aquaculture: low mainte­
and differences in their octanol:water participation coefficient (Kow/ nance, low cost, low battery consumption, and non-metal, robust,
logKow) which is a strong indicator of the behaviour of organic chem­ waterproof, withstand biofouling, and no effects on aquatic organisms
icals in the environment and is used for predicting the distribution of (Parra et al., 2018). Such sensors could be easily adapted for other type
substances in various environmental compartments (water, soil, air, of farm management activities, and integrated as part of the afore­
biota, etc.). Substances with high Kow values tend to adsorb more mentioned on-farm biopurification systems.
readily to organic matter in soils or sediments because of their low af­
finity for water. As indicated in Table S1, the higher Kow value of 5. Conclusion
metolachlor (Kow 794) compared to acetochlor (Kow 300), suggests that
it is likely to bind to the Zn NPs in much the same manner as it would to A suitable and effective green route for synthesis of zero valent
clay particles in soil or suspended solids in water, and indeed this is what ZnNPs in a controllable way, using microwave heating and a mint leaf
is observed experimentally. extract stabilizer is described, that results in nanoscale particles around
36 nm awith cubic closed packing morphology. The UV–Visible absor­
4. Future perspectives bance study determined the reduction in absorbance from the test
analytes, two representative herbicides, which directly shows a decrease
The mechanism of herbicide removal is adsorption, which offers a in the concentration of herbicide in the water samples as a result of
convenient and effective means for purification of drinking water binding to the ZnNPs. The evaluation of the effectiveness of herbicide
without the formation of harmful substances. It is notable that incor­ removal by ZnNPs showed an efficient removal of 99% of metolachlor
poration of the Zn NPs reduces the biofouling of the membranes, thereby and 61% of acetochlor herbicides at a concentration of 0.1 mg Zn NPs
increasing their functional lifetime and available surface area for bind­ per 100 mL of 0.5 g/L herbicide solutions. Incorporation of the syn­
ing of the target herbicides. However, the absorption mechanism means thesized NPs into a polymeric (cellulose acetate) membrane provided
that, despite the high surface area of the Zn NPs, their low-cost pro­ support for the ZnNPs which further decreased the time of adsorption
duction, and the ease of incorporating them into the CA membranes and enhanced the removal of the herbicides from the water samples. The
which allows very high loading values, saturation of the Zn NP surfaces membrane support reduces the potential environmental risks of NP
will inevitably occur after which the membranes will be rendered inef­ release to the environment, and will increase the life-time, activity and
fective. A number of strategies are being explored to address this, re-usability of the ZnNPs. This ecofriendly and cost-effective method­
including the potential for desorption of the herbicides once they have ology opens up new ways of using NP-incorporated membranes for
reached capacity, and then re-deploying the membranes for further water purification, as the green-synthesized ZnNPs are a cheap and
herbicide adsorption. At the local farm scale this could support the effective approach to bind and degrade herbicides. Incorporation of the
recycling and re-use of the recovered herbicides, thus providing addi­ ZnNPs into biodegradable membranes offers an important opportunity
tional environmental benefits. Other areas that are being explored is for real world deployment for remediation of herbicide contaminated
whether the Zn NPs could accelerate the degradation of the bound surface water, and may even offer the potential for on-farm use to
herbicides, as has been reported for alachlor utilizing zero valent iron recover and recycle herbicide run-off in real time, reducing costs for
nanoparticles (Bezbaruah et al., 2009). farmers and reducing environmental impacts from agriculture at source.
Since mineralization is an important step in the degradation of pes­
ticides and herbicides in soil, and involves biological transformation of Declaration of competing interest
organic nitrogen to ammonium nitrogen under aerobic and anaerobic
conditions, future work could explore the potential of the ZnNP-CA The authors declare that they have no known competing financial
membranes as substrates for bacterial activity. To minimize direct interests or personal relationships that could have appeared to influence
pesticide losses from agriculture, the installation of bio purification the work reported in this paper.
systems to treat pesticide-contaminated wastewater on the farm yard
has been proposed (Sniegowski et al., 2011). In on-farm bio-purification Acknowledgements
systems, the contaminated water is conducted over a solid matrix, called
a bio mix, which is composed of a mixture of various materials, for The authors would like to express their gratitude to the Higher ed­
example straw, peat and soil, in which biodegradation and sorption ucation Commission (HEC) Pakistan for granting an IRSIP Scholarship to
result in pesticide removal. Bio-purification systems are considered a Ms. Salma Shad, and to the School of Geography, Earth and Environ­
simple, low-cost, practical and labor-extensive approach for farmers to mental Sciences, University of Birmingham, United Kingdom for hosting
treat pesticide-contaminated water or soil, which suggests there is po­ Ms. Shad and for the technical support for all nanoparticle and
tential for further investigation of the role of the ZnNP-CA membranes as nanoparticle-embedded membrane characterization. We thank Mr.
part of bio-purification systems. Nathan Langford, School of Geography, Earth and Environmental Sci­
The membrane support provides effective removal of pollutants from ences, University of Birmingham, for his help and assistance with AFM
water without releasing NPs into the purified water. The membrane can measurements.
be easily removed from the water source, with capacity for recovery of
the pesticides and re-use. Thus, in the future farmers might themselves Appendix A. Supplementary data
apply the membranes to their own surface water resources for collection
and recycling of the pesticides, if simplified low-cost field-deployable Supplementary data to this article can be found online at https://doi.
devices for determination of pesticide concentrations were available, to org/10.1016/j.clet.2021.100339.
allow re-formulation, and confirm the intact active ingredients rather
than any degradation by-products. Most sensor development is focused

7
S. Shad et al. Cleaner Engineering and Technology 5 (2021) 100339

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