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Sensors Applied for the Detection of Pesticides and Heavy Metals in Freshwaters.

1. Introduction

Seventy-one percent of our planet is covered by water which is a vital necessity to the organisms living on the earth. Even though freshwater only occupied less than 3% of all the water on earth, our daily life is more associated with freshwater than saltwater. However, many freshwater ecosystems have been polluted by anthropogenic activities including the three most dominating contributors: human settlements, industries, and agriculture [1-3]. For example, more than 100,000 chemicals (e.g., pesticides) are registered nowadays, and most of them are related to our daily life; these chemicals can inevitably enter freshwaters [4]. In addition, more than half of the total production of chemicals is harmful to the environment [5]. In Latin America, Africa, and Asia, 1/3, 1/7, and 1/10 of all the streams and rivers have already been affected by pathogen (e.g., fecal coliform bacteria), organic (e.g., biochemical oxygen demand (BOD)), and salinity (e.g., total dissolved solids (TDS)) pollution [6]. At a national scale survey, the water quality of ~1/3 of US' streams and rivers was assessed by the Environmental Protection Agency (EPA), and the results revealed that 55% of the streams were categorized as impaired. Bacteria, sediment, and nutrients were identified as the three most significant causes for stream pollution in this survey [7]. Freshwaters in developing countries such as China are facing more serious pollution situation. It was estimated that ~60% of China's groundwater was classified as poor or very poor, and the number is even higher (~80%) in 17 northern provinces [8]. The impaired water quality negatively affected aquatic organisms and generates major threats to waterbodies, with great consequences on aquatic ecosystems at levels ranging from individuals to watershed [9-13]. More importantly, human health is also at risk if clean drinking water cannot be accessed [4]. It was estimated that the freshwater resources for 82% of the world's population are under high levels of threats, and the situation is more serious in developing countries than in developed countries [14]. Consequently, more than 1/3 of the population in the world lacks safe drinking water [4]. Freshwaters (e.g., streams, rivers, lakes, and ponds) receive large quantity of various pollutants including pesticides [15], heavy metals [16], and nutrients [17]. It was estimated that 80% of municipal wastewater that flows into waterbodies is untreated, and millions of tonnes of heavy metals and other pollutants were dumped into waterbodies every year [18]. In China, human activities introduced 14.5 [+ or -] 3.1 mega tonnes of nitrogen to freshwaters each year which are 2.7 times of the predicted safety threshold [19]. Excess nutrients such as nitrogen and phosphorus in freshwaters usually lead to eutrophication, one of the most common reasons for water quality degradation [20, 21]. Many efforts have been done to improve the water quality of freshwaters via direct or indirect ways [22, 23]. Monitoring water quality in freshwaters is still the first priority for many ecological studies, water quality control, and restoration projects [24, 25].

Monitoring water quality is especially important for the provision of clean drinking water and the protection of aquatic ecosystems [26, 27]. After the development of decades, numerous kinds of sensors, including chemical sensors, biosensors, and electronical sensors, have been developed to detect water quality [28, 29]. A sensor is a device that is capable of providing selective quantitative or semiquantitative analytical information via a biological/chemical/electronical recognition element; it usually is composed of a transducer and a processor [30]. Generally, the requirements of water quality sensors are confined to many factors such as the waterbodies to be monitored, water quality parameters to be tested, and the objects of the monitoring system [31]. The projection of future sensors targets on higher sensitivity, rapider detection, smaller size, inexpensiveness, disposability, ease of manipulation, durability for longer time, and suitability for multiple environments. For example, in a newly published review, Parra et al. [29] summarized several requirements of physical sensors for precision aquaculture: low maintenance, low cost, low battery consumption, nonmetal, robust, waterproof, withstand biofouling, and no effects on aquatic organisms. Previous review papers focus on either one type/category of sensors [32] or one analyte (or one group of analytes) [33]. This review paper will focus on the sensors applied to test two of the most common pollutants in freshwaters, i.e., pesticides and heavy metals. The general contamination status of these parameters in freshwaters and a simple analysis of sensors are also discussed. The sensitivity of sensors (limit of detection (LOD)) and sensor types are especially discussed. The present review paper differs from previous review papers in the following ways: (1) we unified the unit of LOD to make the comparison between studies possible and visualized; (2) only the data collected from freshwaters were used; and (3) not only the sensor types but also the detected analyte categories were discussed.

2. Materials and Methods

2.1. Database Compilation. We build the database of pesticide sensors by searching Web of Science using the following topics: "sensor" and "pesticide or herbicide or fungicide or insecticide" and "freshwater or river or stream or lake or reservoir or pond". Most of the collected papers were published during the last five years which composed almost half of the publications (2015-2019). The data collected before 2015 were mainly based on previous review papers [34-36]. For each publication, we extracted the following information: tested analytes, sensor types (e.g., biosensors and electronical sensors), LODs, and the applicable waterbodies. For the optical sensors, we included fluorescent sensors, luminescent sensors, and colorimetric sensors. The tested analytes were grouped into three categories of pesticides (i.e., herbicides, insecticides, and fungicides). All the units of LODs were unified as ng/ml. The same method was used to build the database of heavy metal sensors by replacing "pesticide OR herbicide OR fungicide OR insecticide" with "heavy metal". For heavy metal sensors, we only collected data during the year 2017-2019 (updated until October) which composed ~1/3 of all the publications.

2.2. Data Analysis. One-way ANOVA (analysis of variation) was conducted to test the differences of LODs among the pesticide groups/heavy metals and among the sensor types. All data were checked for normality before conducting the ANOVA tests and were log-transformed to meet normality and homogeneity assumptions [37]. One case (1.84 * [10.sup.-7]) was deleted from the pesticide sensor dataset due to the outlier when conducting the ANOVA. If significant effects present in the ANOVA, then Tukey's multiple comparison was used for post hoc analysis of significant differences among sensor types or analyte groups [38]. All statistical analyses were carried out using SPSS 24.0.

3. Results and Discussion

3.1. Pesticide Sensors

3.1.1. Pesticides in Freshwaters. Pesticides are usually classified into three major categories: herbicides, insecticides, and fungicides/bactericides. The application of pesticides is used to control weeds, pest outbreaks, and fungal infestations for the security of global food supply [15, 39, 40]. The worldwide pesticide expenditures increased from $48.8 billion in 2008 to $55.9 billion in 2012 [41]. After application, these pesticides can enter freshwaters via numerous ways such as wastewater effluent and surface runoff [15]. In a national (US) monitoring network for pesticides in streams and rivers during 1992-2011, the concentrations of one or more pesticides exceeded the aquatic organism benchmark in 61%-69%, 45%, and 53%90% of the streams in agricultural, mixed-land-use, and urban areas, respectively [42]. In Europe, atrazine (herbicide) is among the most frequently detected chemicals in groundwaters [5]. Due to their high frequency of being detected in freshwaters and the toxicity effects on aquatic organisms, pesticides are one of the most common monitored water quality parameters [43-45]. During the last few decades, many sensors have been developed to detect pesticides in freshwaters [46, 47].

Most of the sensor data we collected can be applied in rivers and streams which correspond to the fact that most studies focused on these waterbodies and indicated the needs to monitoring pesticides in streams and rivers. The most frequently detected pesticides are paraquat, followed by atrazine and carbaryl (Table 1). This result is in accordance with the most common pesticide contamination in freshwaters [5]. However, only three studies detected glyphosate [48-50], the most widely used herbicide worldwide [51, 52]. Therefore, more studies should target on the development of glyphosate sensors to get a clearer understanding of the glyphosate contamination in freshwaters. Although the production of herbicides is the highest worldwide [53], more studies focus on insecticide sensors than herbicide sensors (Table 1), probably because organophosphorus pesticides, the most frequently detected analytes, are highly toxic to organisms [54]. Therefore, priority was given to those with relatively high toxicity rather than those used in large quantity when monitoring water quality.

3.1.2. Sensitivity of Pesticide Sensors. The average LOD of pesticide sensors included in this review was 72.53 [+ or -] 12.69 ng/ml (n =180, mean [+ or -] SE). Not all of sensors for the detection of pesticides in freshwaters were sensitive enough for ecological and monitoring requirements. The proposed maximum contaminant level, i.e., the maximum permissible level (MCL) of a contaminant in water that is delivered to any user of a public waterbody, for many pesticides (e.g., atrazine and aldicarb) is at the level of ng/ml or even less than 1 ng/ml [170]. For example, the criterion maximum concentrations (CMC) of carbaryl, chlorpyrifos, diazinon, and parathion for aquatic life in freshwaters of the United States are 2.1, 0.083, 0.17, and 0.065 ng/ml, respectively (Table 2). Moreover, more than 5% of the MCLs for the top 29 commonly regulated pesticides in drinking water exceed the computed upper thresholds for human health risk uncertainty [171], which means that the MCLs for pesticides in drinking water should be stricter and higher sensitive sensors are needed. However, our results indicated that the LODs for 32.8% of the sensors are higher than 10 ng/ml, and <50% of the sensors can reach the level of 3 ng/ml. Therefore, many sensors may not be sensitive enough for the detection of pesticides in freshwaters regarding the requirements for the protection of aquatic life and human health. In addition, there are more than 1,000 pesticides used worldwide to ensure food security. Nevertheless, this review paper only included 97 kinds of pesticides/active ingredients which cover less than 10% of all pesticides. Therefore, future studies should focus on the largely ignored pesticides because many pesticides have toxic effects on aquatic organisms [172] and human health [173, 174]. For example, many sensors were developed to analyze organophosphorus pesticides (e.g., chlorpyrifos and carbaryl) while fewer sensors were targeted on organochlorine pesticides such as dichlorodiphenyltrichloroethane (DDT). DDT was widely used for the control of pest and fungus in the last century. Even though DDT has been banned for decades in many countries, it can still be found in 8-100% of the sampled small streams in three South American countries [175]. Therefore, DDT is still a global concern due to the toxicity, not easy to be degraded, and the tendency to be accumulated in organisms [176]. The LOD of one biooptical sensor used for the detection of DDT in river water can be as low as 0.015ng/ml [177].

LODs in this study showed thousands of orders for different analytes and sensors. Among all the sensors been checked, the most sensitive sensor was developed by Kumar et al. [131], in which the indirect detection of malathion through an enzyme-based fluorometric method was applied. This system can achieve an ultrasensitive LOD which is as low as 1.84 * [10.sup.-7] ng/ml and can be spiked for lake water and agricultural runoff water [131]. By contrast, some sensors are relatively "insensitive" with the LODs at the level of 100 ng/ml [50, 122, 141]. Although, the average LOD for herbicide sensors is higher than that of insecticides and fungicides, there is no significant difference among the three categories of pesticides ([F.sub.2,176] = 2.717, P = 0.069, Figure 1). The sensitivity of sensors collected in this paper is similar to that of previous review papers [34, 178]. Only 22 cases (12.22%) were related to fungicide sensors. This extremely low percentage indicated the urgency to improve the monitoring of fungicides in freshwaters, because fungicides are widely occurring in freshwaters and are highly toxic to numerous aquatic organisms [15, 179]. For the sensor types, we found a similar pattern (Table 1) as some previous review papers that electrochemical [180], optical [33, 35], and biological [181] sensors are among the most widely used sensors for the detection of pesticides in freshwaters. Regarding the sensitivity of different types of sensors, biosensors showed the highest sensitivity compared with other sensors, while the biooptical and electrochemical optical sensors indicated the lowest sensitivity ([F.sub.9,169] = 7.239, P <0.001, Figure 2). Biosensors have been widely used in the environmental monitoring [5], given the advantages of biosensors in detecting pesticides and other pollutants over conventional methods: high stability (e.g., they can operate at high temperature), inexpensiveness, possibility for real-time monitoring, high electivity, and disposability, just to name some of them

[181-183]. Biosensors could be a promising direction for pesticide detection in freshwaters. For example, diatoms, which were popular for the assessment of water quality [184], may be a suitable tool for biosensors.

3.2. Heavy Metal Sensors

3.2.1. Heavy Metals in Freshwaters. Heavy metals refer to metallic elements that have a high atomic weight and with a density of at least five times greater than that of water [185]. Aquatic ecosystems can be polluted by heavy metals through multiple ways such as mining, weathering of soils and rocks, industrial wastewater, and surface runoff [186-188]. Natural concentrations of Pb and Cd are less than 0.003 ng/ml in streams [189]. However, heavy metal concentrations may be two or three orders of the natural concentrations or even higher in polluted waterbodies [190, 191]. The most common heavy metal pollutants found in aquatic ecosystems are As, Cd, Cr, Cu, Ni, Pb, Hg, and Zn [192]. For instance, Cu, Fe, Zn, Mn, and Cr were the top five heavy metals of concern in freshwaters in Bohai Region, China, while Hg showed the lowest risk [193]. The concentrations of many heavy metals in the river Ganga water and sediment exceeded the acceptable concentrations and threatened human health and aquatic organisms [194]. Three countries, i.e., the United States, Germany, and Russia, consume 3/4 of the world's most widely used metals. Human health and aquatic ecosystems can be threatened by heavy metals especially by Pb, Cd, Hg, and As [195, 196]. For example, groundwaters contaminated by As threatened millions of people's drinking water safety in developing countries such as India, Cambodia, and Vietnam [4]. Aquatic organisms still suffer from the toxic effects of heavy metals even though upstream mining activities ceased for decades [197]. Due to the high toxicity and them commonly found in freshwaters [198, 199], heavy metals are among the most important indices when monitoring water quality [45, 200].

3.2.2. Sensitivity of Heavy Metal Sensors. Altogether, 61 publications were selected during the years 2017-2019 (the data were updated until October 2019), with nine types of sensors used for the detection of 13 heavy metals in freshwaters (Table 3). The average LOD for all sensors is 65.36 [+ or -] 47.51 ng/ml (n = 117, mean [+ or -] SE). The sensitivity of sensors differed among the detected heavy metals ([F.sub.9,104] = 2.289, P = 0.022, Figure 3). Sensors targeted on Ag had the highest sensitivity while the sensors used to detect Fe and Cr showed the lowest sensitivity. The sensitivity of many sensors can satisfy the requirements for drinking water and wild life protection. The LODs of some sensors were still higher than CMCs or MCLs. Especially for mercury sensors, 30% of the collected sensors failed to satisfy the CMC or MCL requirements. It reminds us that higher sensitivity sensors should be developed to protect human health and aquatic organisms. In addition, the CMC/MCL may be changed due to the national regulation [201, 202] which means that the higher sensitivity sensors may be needed to detect lower concentrations of heavy metals. As mentioned above, As, Cr, Ni, and Zn are among the highest concentrations of heavy metals in freshwaters [192]. However, limited sensors were developed to detect these heavy metals. Therefore, more diverse sensors should be developed to analyze these heavy metals.

Regarding the sensor types, more than half of the heavy metal sensors were based on electrochemical methods, while few studies applied biological ways (Table 3). The sensitivity of sensors for heavy metal detection varied among sensor types ([F.sub.8,108] = 12.5, P < 0.001, Figure 4). Bioelectrochemical sensors had the highest sensitivity, while bioelectronical sensors showed the lowest sensitivity. The most sensitive sensor was a bioelectrochemical sensor which was developed by Zhang et al. [251] for the detection of silver in tap and lake water, and the LOD was as low as 5.0 * [10.sup.-8] ng/ml. On the contrary, a pigment-based whole-cell biosensor developed for the analysis of copper in pond and tap water showed the highest LOD (5547.6 ng/ml) [262]. The average LOD of heavy metals based on electrochemical methods was 12.187 [+ or -] 5.446ng/ml (n = 65, mean [+ or -] SE). The LOD of electrochemical sensors in this review is higher than the LODs of electrochemical sensors in previous review papers [210, 263, 264]. This probably is because the LODs of four electrochemical sensors were higher than 50 ng/ml which increased the average LOD. Electrochemical sensors have the advantages such as easy to manipulate, cheap, suitable for field monitoring, and portable which make it suitable for heavy metal detection [263]. However, the optical sensors in this review did not show higher sensitivity than electrochemical sensors as mentioned in a previous study [263]. This is caused by two studies which used colorimetric and luminescent detection; the LODs in these two studies are 30-300 ng/ml [209, 255].

4. Conclusion

This review presents the general information on sensors for the detection of pesticides and heavy metals in freshwaters. The studied sensors covered less than 10% of all registered pesticides/ingredients. Most of the selected pesticide sensors were used to analyze insecticides and herbicides while limited studies were focused on fungicides. The LODs of ~30% of the pesticide sensors failed to meet the maximum permissible concentrations for aquatic life and drinking water. Biosensors showed the highest sensitivity and appeared to be a promising technology in future development for the detection of pesticides in freshwaters. The average LOD of sensors for the detection of heavy metals is 65.36 ng/ml during the last three years. The LODs of a small fraction of sensors such as mercury sensors were higher than the upper threshold concentrations for the protection of wild life and drinking water safety. Most of the heavy metal sensors were designed to detect mercury, cadmium, lead, and copper based on electrochemical methods. These results imply us that higher sensitivity sensors should be developed in the future. In addition, future sensors should cover more pesticides and heavy metals (e.g., glyphosate and zinc) which are commonly detected in waterbodies and are highly toxic to aquatic organisms and human health.

https://doi.org/10.1155/2020/8503491

Conflicts of Interest

The authors declare that there is no conflict of interest regarding the publication of this paper.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant numbers 41501566 and 41601576), Fundamental Research Funds for the Central Universities (grant number 2412018JC002), Program of Introducing Talents of Discipline to Universities (grant number B16011), Foundation of Education Department of Jilin Province (grant number 2014 B050), and Basal Research Fund for Undergraduate Universities of Heilongjiang Province of China (grant number 2019-KYYWF-0598).

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Hongyong Xiang [ID], (1,2) Qinghua Cai, (3) Yuan Li [ID], (4) Zhenxing Zhang, (1,5) Lina Cao, (6) Kun Li, (7) and Haijun Yang [ID] (1,2,8)

(1) Key Laboratory of Vegetation Ecology, Ministry of Education, Institute of Grassland Science, Northeast Normal University, Changchun, Jilin 130024, China

(2) Institute for Ecological Research and Pollution Control of Plateau Lakes, School of Ecology and Environmental Science, Yunnan University, Kunming, Yunnan 650500, China

(3) State Key Laboratory of Freshwater Ecology and Biotechnology, Institute of Hydrobiology, Chinese Academy of Sciences, Wuhan 430072, China

(4) Northwest Land and Resources Research Center, Shaanxi Normal Northwest University, China

(5) State Environmental Protection Key Laboratory of Wetland Ecology and Vegetation Restoration, Northeast Normal University, Changchun, Jilin 130024, China

(6) Ecology and Environment Department of Jilin Province, Changchun, Jilin 130024, China

(7) Heilongjiang Provincial Key Laboratory of Ecological Restoration and Resource Utilization for Cold Region, Heilongjiang University, Harbin 150080, China

(8) School of Life Science and Geology, Yili Normal University, Yili, Xinjiang 835000, China

Correspondence should be addressed to Zhenxing Zhang; zhangzx725@nenu.edu.cn and Haijun Yang; yang@nenu.edu.cn

Received 29 October 2019; Accepted 20 January 2020; Published 11 February 2020

Academic Editor: Alberto J. Palma

Caption: Figure 1: Averages of limit of detection of sensors for herbicides, insecticides, and fungicides. Values are the mean [+ or -] SE.

Caption: Figure 2: Averages of limit of detection of pesticide sensors based on different detection methods. Values are the mean [+ or -] SE. Different uppercase letters above each bar indicate significant differences after one-way ANOVA and post hoc Tukey (parameters with the same letter are not significantly different between sensors).

Caption: Figure 3: Averages of limit of detection of sensors for the detection of heavy metals in freshwaters. Values are the mean [+ or -] SE. Different uppercase letters above each bar indicate significant differences after one-way ANOVA and post hoc Tukey (parameters with the same letter are not significantly different between heavy metal sensors). Only one sensor was included in this review for the detection of Al, Mn, and Fe. Therefore, these three heavy metal sensors were excluded from the ANOVA. The data of [Cr.sup.3+] and [Cr.sup.6+] were combined for the ANOVA.

Caption: Figure 4: Averages of limit of detection of heavy metal sensors based on different methods. Values are the mean [+ or -] SE. Different uppercase letters above each bar indicate significant differences after one-way ANOVA and post hoc Tukey (parameters with the same letter are not significantly different between sensors).
Table 1: Summary of studies employing sensors for the detection of
pesticides in freshwaters.

Analytes                        Sensor types       LOD (ng/ml)

Picloram                     Bioelectrochemical         5
Malathion                         Biosensor             1
Methamidophos                     Biosensor           0.01
                                                      0.013
Monocrotophos                                         0.015
Mevinphos                         Biosensor           0.009
Phosphamidon                                          0.012
Omethoate                                             0.032
Bentazone                       Electronical          262.3
Carbaryl                                               5.3
Heptenophos                    Electrochemical         3.6
Fenitrothion                                           160
Carbofuran                      Electronical            2
Fenobucarb                                              2
Paraoxon                       Bioelectronical         2.8
Carbaryl                                               8.0
Chlorpyrifos                      Biosensor           0.004
Chlorfenvinfos                                        0.004
Atrazine                       Electrochemical         2.2
Atrazine                       Electrochemical         4.5
Atrazine                       Electrochemical         1.9
Atrazine                       Electrochemical         13
Atrazine                       Electrochemical         3.1
Ametryne                                               3.8
Atrazine                       Electrochemical        30.2
Chlorpyrifos oxon                                      1.1
Paraoxon                       Bioelectronical         30
Malaoxon                                               25
Chlormequat                    Bioelectronical       502.74
Carbofuran                     Bioelectronical         20
Carbaryl                                               300
Paraoxon                       Bioelectronical         5.5
Methyl parathion                                       5.8
Omethoate                      Bioelectronical        21.3
Atrazine                         Biooptical           0.15
Isoproturon                        Bio-Opt              3
Carbaryl                         Biooptical           0.029
Carbendazim                                            15
Carbofuran                       Biooptical            68
Benomyl                                                35
Carbaryl                         Biooptical           0.27
Fuberidazole                                          0.09
Carbaryl                         Biooptical             6
Benomyl                                                 9
Fuberidazole                     Biooptical           0.18
O-Phenylphenol                                         6.1
Linuron                          Biooptical            130
Metsulfuron methyl                 Optical            0.14
[alpha]-Naphthol                                        2
O-Phenylphenol                     Optical              2
Thiabendazole                                           2
Triazine                         Biooptical          0.0013
Thiabendazole                      Optical             2.8
Warfarin                           Optical              2
Thiabendazole                      Optical             2.5
Metsulfuron methyl                                     3.3
N-1-Naphthylphthlamic acid                             8.1
1-Naphthylamine                                       11.2
Thiabendazole                      Optical             4.5
Carbaryl                         Biooptical           1.38
1-Naphthylamine                    Optical             1.1
Paraquat                           Optical            0.11
Paraquat                           Optical             1.6
Paraquat                           Optical            0.003
Paraquat                           Optical             0.7
Paraquat                     Bioelectrochemical       0.926
Paraquat                         Biooptical           0.036
Paraquat                        Electronical          23.92
Paraquat                        Electronical            2
Paraquat                           Optical             22
Paraquat                         Ele-optical           0.1
Diquat                                                 0.2
Paraquat                         Ele-optical           0.2
Diquat                                                 0.1
Paraquat                         Ele-optical            5
Diquat                                                  1
Dipterex                                              5.152
Dursban                                               7.012
Paraquat                         Che-optical          5.143
Methyl thiophanate                                    6.84
Cartap                                                5.476
Paraoxon                           Optical            0.05
Diniconazole                     Biooptical            6.4
Diuron                         Electrochemical       0.00125
Diazinon                                              36.3
Iprobenfos                       Biooptical           53.6
Edifenphos                                            27.9
Paraoxon                                                2
2,4-D                          Bioelectronical         50
Atrazine                                               10
Diazinon                     Bioelectrochemical       0.039

Metamitron                     Electrochemical        7.28
Carbamate                        Biooptical            3.3
Diuron                       Bioelectrochemical        2.1
Mesotrione                     Electrochemical        8.822
Paraquat                       Electrochemical        3.086
Fenoxanil                       Electronical         0.0092
Malathion                                             0.01
Parathion methyl             Bioelectrochemical       0.02
Monocrotophos                Bioelectrochemical       0.01
Dichlorvos                                            0.01
Dicloran                     Bioelectrochemical       0.099
Fenitrothion                   Electrochemical        0.036
Carbamate                          Optical            0.023
Fenoxycarb                       Biooptical          949.221
Malathion                        Ele-optical         0.0991
Methomyl                        Electronical         126.192
Diuron                                               8.1585
2,4-D                           Electronical         26.405
Tebuthiuron                                          77.625
Pyrethroids                      Biooptical           42.64
2,4-D                           Electronical         44.008
Fomesafen                      Electrochemical         89
Glyphosate                                             338
Dimethoate                                           458.52
Atrazine                                             431.36
Cyanazine                                            481.39
Diuron                                                466.2
Imidacloprid                                         511.32
Malathion                                            660.72
Imazethapyr                      Biooptical            578
Mecoprop-P                                            429.3
2,4-D                                                440.08
Trifluralin                                          670.56
Paraquat                                             514.32
Metolachlor                                           567.6
Carbaryl                                             402.44
Acephate                                               366
Dichlorophen                    Electronical          3.768
Hexazinone                     Bioelectronical       0.00066
Malathion                          Optical         1.84 x 10-7
Fenitrothion                       Optical            1.677
Pendimethalin                   Electronical         10.408
Metol                          Electrochemical        0.344
Bisphenol A                                           0.685
Azinphos methyl                  Che-optical          0.549
Fenvalerate pyrethroid             Optical            0.01
Propham                        Electrochemical        0.789
Propham                        Electrochemical        0.179
Cyanazine                      Electrochemical        0.06
Tau-fluvalinate                  Biooptical           6.105
Methyl parathion                   Optical            291.3
Pymetrozine                        Optical            2.172
Imidacloprid                    Electronical          106.1
Pyrethroid                       Biooptical           6.568
Paraquat                        Electronical           0.8
Clopyralid                     Electrochemical        0.154
Carbendazim                     Electronical         37.473
Quinalphos                     Electrochemical        0.378
Methyl parathion                 Biooptical           1.87
2,4-D                              Optical           0.0045
Diethofencarb                   Electronical           320
Diazinon                     Bioelectrochemical      57.827
Naptalam                       Electrochemical        4.37
Phosmet                          Biooptical          0.0004
Phoxim                           Che-optical         298.298
Bentazone                      Electrochemical        8.918
Fenitrothion                    Electronical          0.155
Chlorpyrifos                 Bioelectrochemical       0.07
Lindane                          Ele-optical          0.585
Difenzoquat                    Electrochemical       102.225
Diquat                         Electrochemical       37.844
Methyl parathion                   Optical           27.674
Glyphosate                         Optical            5.07
Aminomethylphosphonic acid                            1.666
Atrazine                                             25.882
Chlorpyrifos                                         10.167
Lindane                      Opt-electrochemical     40.716
Tetradifon                                           14.242
Imidacloprid                                          3.322
Glyphosate                         Optical             845
Methyl parathion               Electrochemical        0.012
Amitrole                       Electrochemical       58.856
Paraoxon                                              0.014
Malathion                          Optical            0.033
Methamidophos                                         0.017
Carbaryl                                              0.026
Fenitrothion                    Electronical         0.0526
Carbendazim                    Electrochemical        5.736
Ofloxacin                          Optical            0.123

Analytes                                    Waterbodies

Picloram                                 Paddy field water
Malathion                                    Tap water
Methamidophos                                Tap water
                                            River water
Monocrotophos
Mevinphos                               River and tap water
Phosphamidon
Omethoate
Bentazone                                   River water
Carbaryl
Heptenophos                                 Wastewater
Fenitrothion
Carbofuran                         Tap water and farmland water
Fenobucarb
Paraoxon                                   Lagoon water
Carbaryl
Chlorpyrifos                                Lake water
Chlorfenvinfos
Atrazine                                    River water
Atrazine                                    River water
Atrazine                                    River water
Atrazine                                    River water
Atrazine                                    River water
Ametryne
Atrazine                                  Natural waters
Chlorpyrifos oxon
Paraoxon                                    River water
Malaoxon
Chlormequat                           River and ground water
Carbofuran                                  Well water
Carbaryl
Paraoxon                                    Well water
Methyl parathion
Omethoate                                   Lake water
Atrazine                                Drinking, lake, and
                                      agricultural wastewater
Isoproturon                                 Well water
Carbaryl                                  Drinking water
Carbendazim
Carbofuran                              Environmental water
Benomyl
Carbaryl                                    River water
Fuberidazole
Carbaryl                        River, well, dam, irrigation water
Benomyl
Fuberidazole                           River and well water
O-Phenylphenol
Linuron                                  Tap, underground,
                                     mineral, and river water
Metsulfuron methyl               River, well, and irrigation water
[alpha]-Naphthol
O-Phenylphenol                          Tap and river water
Thiabendazole
Triazine                                    River water
Thiabendazole                            Tap, underground,
                                     mineral, and river water
Warfarin                           River, lake, and spring water
Thiabendazole                    Well, river, and irrigation water
Metsulfuron methyl
N-1-Naphthylphthlamic acid          Drinking and mineral water
1-Naphthylamine
Thiabendazole                            Tap, underground,
                                     mineral, and river water
Carbaryl                         Groundwater, tap, and river water
1-Naphthylamine                   Well, tap, and urban wastewater
Paraquat                      Tap, well, lake, river, and rain water
Paraquat                                    Wastewater
Paraquat                       Tap, mineral, waste, and ground water
Paraquat                                  Drinking water
Paraquat                               River and groundwater
Paraquat                                    River water
Paraquat                                    River water
Paraquat                             Dam, river, and tap water
Paraquat                           River, dam, and mineral water
Paraquat                                    River water
Diquat
Paraquat                                 Tap, lake, river,
Diquat                                 ground, and bog water
Paraquat
Diquat
Dipterex
Dursban
Paraquat                                    Wastewater
Methyl thiophanate
Cartap
Paraoxon                                Tap and river water
Diniconazole                           River and wastewater
Diuron                                      Lake water
Diazinon
Iprobenfos                                  River water
Edifenphos
Paraoxon
2,4-D                                       River water
Atrazine
Diazinon                                      Tap and
                                         river wastewater
Metamitron                                  River water
Carbamate                                   Lake water
Diuron                                      River water
Mesotrione                              Lake and tap water
Paraquat                                    River water
Fenoxanil                                   River water
Malathion
Parathion methyl                        Tap and river water
Monocrotophos
Dichlorvos
Dicloran                                Tap and river water
Fenitrothion                            Tap and lake water
Carbamate                                   River water
Fenoxycarb                                  River water
Malathion                                   Pond water
Methomyl                                River and tap water
Diuron
2,4-D                                   Lake and well water
Tebuthiuron
Pyrethroids                                 River water
2,4-D                                       River water
Fomesafen                                   Lake water
Glyphosate
Dimethoate
Atrazine
Cyanazine
Diuron
Imidacloprid
Malathion
Imazethapyr                                 Lake water
Mecoprop-P
2,4-D
Trifluralin
Paraquat
Metolachlor
Carbaryl
Acephate
Dichlorophen                                River water
Hexazinone                                  River water
Malathion                    Agricultural runoff water and lake water
Fenitrothion                        Well, river, and tap water
Pendimethalin                           Tap and river water
Metol                                       River water
Bisphenol A
Azinphos methyl                         Tap and river water
Fenvalerate pyrethroid                   Tao, river, well,
                                   distilled, and draining water
Propham                                     River water
Propham                                     River water
Cyanazine                          Tap, river, and ground water
Tau-fluvalinate                             Lake water
Methyl parathion                            Lake water
Pymetrozine                             Tap and lake water
Imidacloprid                                River water
Pyrethroid                                  River water
Paraquat                                    River water
Clopyralid                                  River water
Carbendazim                                 River water
Quinalphos                              Tap and lake water
Methyl parathion                            River water
2,4-D                               Tap, bottle, and lake water
Diethofencarb                               River water
Diazinon                                    River water
Naptalam                                    River water
Phosmet                                     Lake water
Phoxim                                      River water
Bentazone                              Lake and ground water
Fenitrothion                                Well water
Chlorpyrifos                                Lake water
Lindane                                 River and tap water
Difenzoquat                          River and deionized water
Diquat                               River and drinking water
Methyl parathion                            Pond water
Glyphosate                                  Lake water
Aminomethylphosphonic acid
Atrazine
Chlorpyrifos
Lindane                                     River water
Tetradifon
Imidacloprid
Glyphosate                                  River water
Methyl parathion                            River water
Amitrole                                    River water
Paraoxon
Malathion                               Tap and river water
Methamidophos
Carbaryl
Fenitrothion                                River water
Carbendazim                                 River water
Ofloxacin                               River and tap water

Analytes                     Ref.

Picloram                     [55]
Malathion                    [56]
Methamidophos                [57]
Monocrotophos
Mevinphos                    [58]
Phosphamidon
Omethoate
Bentazone                    [59]
Carbaryl
Heptenophos                  [60]
Fenitrothion
Carbofuran                   [61]
Fenobucarb
Paraoxon                     [62]
Carbaryl
Chlorpyrifos                 [63]
Chlorfenvinfos
Atrazine                     [64]
Atrazine                     [65]
Atrazine                     [66]
Atrazine                     [67]
Atrazine                     [68]
Ametryne
Atrazine                     [69]
Chlorpyrifos oxon
Paraoxon                     [70]
Malaoxon
Chlormequat                  [71]
Carbofuran                   [72]
Carbaryl
Paraoxon                     [73]
Methyl parathion
Omethoate                    [74]
Atrazine                     [75]
Isoproturon                  [76]
Carbaryl                     [77]
Carbendazim
Carbofuran                   [78]
Benomyl
Carbaryl                     [79]
Fuberidazole
Carbaryl                     [80]
Benomyl
Fuberidazole                 [81]
O-Phenylphenol
Linuron                      [82]
Metsulfuron methyl           [83]
[alpha]-Naphthol
O-Phenylphenol               [84]
Thiabendazole
Triazine                     [85]
Thiabendazole                [86]
Warfarin                     [87]
Thiabendazole                [88]
Metsulfuron methyl
N-1-Naphthylphthlamic acid   [89]
1-Naphthylamine
Thiabendazole                [90]
Carbaryl                     [91]
1-Naphthylamine              [92]
Paraquat                     [93]
Paraquat                     [94]
Paraquat                     [95]
Paraquat                     [96]
Paraquat                     [97]
Paraquat                     [98]
Paraquat                     [99]
Paraquat                     [100]
Paraquat                     [101]
Paraquat                     [102]
Diquat
Paraquat                     [103]
Diquat
Paraquat                     [104]
Diquat
Dipterex
Dursban
Paraquat                     [105]
Methyl thiophanate
Cartap
Paraoxon                     [106]
Diniconazole                 [107]
Diuron                       [108]
Diazinon
Iprobenfos                   [109]
Edifenphos
Paraoxon
2,4-D                        [110]
Atrazine
Diazinon                     [111]
Metamitron                   [112]
Carbamate                    [113]
Diuron                       [114]
Mesotrione                   [115]
Paraquat                     [116]
Fenoxanil                    [117]
Malathion
Parathion methyl             [118]
Monocrotophos
Dichlorvos
Dicloran                     [119]
Fenitrothion                 [120]
Carbamate                    [121]
Fenoxycarb                   [122]
Malathion                    [123]
Methomyl                     [124]
Diuron
2,4-D                        [125]
Tebuthiuron
Pyrethroids                  [126]
2,4-D                        [127]
Fomesafen                    [128]
Glyphosate
Dimethoate
Atrazine
Cyanazine
Diuron
Imidacloprid
Malathion
Imazethapyr                  [50]
Mecoprop-P
2,4-D
Trifluralin
Paraquat
Metolachlor
Carbaryl
Acephate
Dichlorophen                 [129]
Hexazinone                   [130]
Malathion                    [131]
Fenitrothion                 [132]
Pendimethalin                [133]
Metol                        [134]
Bisphenol A
Azinphos methyl              [135]
Fenvalerate pyrethroid       [136]
Propham                      [137]
Propham                      [138]
Cyanazine                    [139]
Tau-fluvalinate              [140]
Methyl parathion             [141]
Pymetrozine                  [142]
Imidacloprid                 [143]
Pyrethroid                   [144]
Paraquat                     [145]
Clopyralid                   [146]
Carbendazim                  [147]
Quinalphos                   [148]
Methyl parathion             [149]
2,4-D                        [150]
Diethofencarb                [151]
Diazinon                     [152]
Naptalam                     [153]
Phosmet                      [154]
Phoxim                       [155]
Bentazone                    [156]
Fenitrothion                 [157]
Chlorpyrifos                 [158]
Lindane                      [159]
Difenzoquat                  [160]
Diquat                       [161]
Methyl parathion             [162]
Glyphosate                   [48]
Aminomethylphosphonic acid
Atrazine
Chlorpyrifos
Lindane                      [163]
Tetradifon
Imidacloprid
Glyphosate                   [49]
Methyl parathion             [164]
Amitrole                     [165]
Paraoxon
Malathion                    [166]
Methamidophos
Carbaryl
Fenitrothion                 [167]
Carbendazim                  [168]
Ofloxacin                    [169]

Table 2: Criterion maximum concentration and maximum
contaminant concentration of some pesticides and heavy metals in
freshwaters in the United States.

                    CMCs (ng/ml)   MCLs (ng/ml)

Pesticides
Carbaryl                2.1             --
Chlorpyrifos           0.083            --
Diazinon                0.17            --
Parathion              0.065            --
Dieldrin                0.24            --
Lindane                 0.95           0.2
Atrazine                 --             3
2,4-D                    --             70
Diquat                   --             20
Heavy metals
Arsenic              340 (1.0)          10
Cadmium              1.8 (1.14)         5
[Chromium.sup.3+]   570 (0.316)         50
[Chromium.sup.6+]    16 (0.982)         50
Copper                -(0.96)          130
Lead                 82 (1.46)          15
Mercury              1.4 (0.85)         2
Nickel              470 (0.998)         --
Silver               3.2 (0.85)        100
Zinc                120 (0.978)        500

Note: CMC: criterion maximum concentration for the recommended aquatic
life in the United States. Numbers in parentheses of CMCs for heavy
metals are conversion factors for dissolved metals. MCL: maximum
contaminant limit concentration for drinking water in the United
States.

Table 3: Summary of sensors used to detect heavy metals in freshwaters
during the year 2017-2019.

Analytes               Sensors            LOD (ng/ml)

[As.sup.3+]           Biosensor              0.005
[As.sup.3+]        Electrochemical            75
[Cd.sup.2+]        Electrochemical           0.068
[Pb.sup.2+]                                  0.105
[Pb.sup.2+]        Electrochemical           0.15
[Pb.sup.2+]            Optical               0.029
[Hg.sup.2+]                                  0.044
[Cu.sup.2+]        Electrochemical           9.532
[Fe.sup.3+]                                   200
[Ni.sup.2+]                                   300
[Cr.sup.6+]            Optical                100
[Cu.sup.2+]                                   30
[Al.sup.3+]                                   80
[Zn.sup.2+]                                   40
[Cd.sup.2+]        Electrochemical           0.337
[Pb.sup.2+]                                   0.2
[Cu.sup.2+]        Electrochemical            0.2
[Hg.sup.2+]                                   0.2
[Pb.sup.2+]        Electrochemical            0.6
[Cu.sup.2+]                                   0.3
[Ag.sup.+]            Biosensor              0.006
[Cd.sup.2+]                                 0.0056
[Pb.sup.2+]        Electrochemical          0.0166
[Cu.sup.2+]                                  0.001
[Hg.sup.2+]                                  0.010
[As.sub.3+]   Electrochemical biosensor    0.000003
[Cd.sup.2+]        Electrochemical           0.17
[Hg.sup.2+]            Optical                0.6
[Pb.sup.2+]        Electrochemical           0.17
[Cd.sup.2+]                                  0.21
[Hg.sup.2+]        Electrochemical           6.018
[Cu.sup.2+]                                  0.02
[Pb.sup.2+]         Electronical             0.03
[Cr.sup.3+]                                  0.15
[Ag.sup.+]         Electrochemical           0.098
[Hg.sup.2+]        Biofluorescent            0.261
[Cd.sup.2+]        Electrochemical           0.05
[Ni.sup.2+]        Electrochemical           0.12
[Cu.sup.2+]                                    3
[Cd.sup.2+]        Electrochemical             4
[Pb.sup.2+]                                   2.5
[Cd.sup.2+]                                  1.012
[Pb.sup.2+]        Electrochemical           0.207
[Cu.sup.2+]                                  0.508
[Hg.sup.2+]                                  0.181
[Ni.sup.2+]                                   240
[Cr.sup.6+]        Electrochemical            180
[Hg.sup.2+]                                   190
[Pb.sup.2+]        Electrochemical            0.5
[Hg.sup.2+]            Optical               0.261
[As.sup.3+]          Biooptical              0.005
[Hg.sup.2+]          Biooptical              0.241
[Pb.sup.2+]      Bioelectrochemical        0.000001
[Cd.sup.2+]        Electrochemical           3.372
[Hg.sup.2+]            Optical               7.422
[Cu.sup.2+]                                  6.672
[Pb.sup.2+]                                  0.15
[Cu.sup.2+]        Electrochemical           0.07
[Hg.sup.2+]                                  0.13
Pb                 Electrochemical           1.68
Cd                                           1.24
[Cu.sup.2+]            Optical              0.0064
[Fe.sup.3+]                                  0.056
[Pb.sup.2+]          Biooptical              1.036
[Hg.sup.2+]                                  3.731
[Cd.sup.2+]        Electrochemical           1.16
                                             0.152
[Pb.sup.2+]            Optical               0.216
[Pb.sup.2+]            Optical               0.011
[As.sup.3+]        Bioelectronical           2.248
[Cd.sup.2+]                                  7.869
[Cd.sup.2+]                                   0.5
[Pb.sup.2+]        Electrochemical             1
[Cu.sup.2+]                                    5
[Cr.sup.3+]           Biosensor              0.35
[Pb.sup.2+]        Electrochemical           4.144
[Cd.sup.2+]        Electrochemical           7.45
[Pb.sup.2+]                                  1.17
[Zn.sup.2+]                                  0.327
[Cd.sup.2+]        Electrochemical           0.225
[Pb.sup.2+]                                  0.166
[Cu.sup.2+]        Electrochemical          25.418
[Cd.sup.2+]                                 0.0025
[Pb.sup.2+]        Electrochemical          0.0518
[Ni.sup.2+]                                 0.0002
[Zn.sup.2+]                                  0.05
[Pb.sup.2+]        Electrochemical           0.02
[Cu.sup.2+]                                  0.03
[Pb.sup.2+]        Electrochemical           2.486
[Ag.sup.+]       Bioelectrochemical       0.00000005
[Cd.sup.2+]        Electrochemical            0.2
[Pb.sup.2+]                                   0.3
[Pb.sup.2+]        Bioelectronical           3.937
[Hg.sup.2+]                                  3.611
[Cu.sup.2+]        Electrochemical          19.064
[Pb.sup.2+]                                 192.696
[Cr.sup.3+]            Optical              48.356
[Hg.sup.2+]                                 186.549
[Cd.sup.2+]                                  0.001
[Cu.sup.2+]           Chemical               0.006
[Hg.sup.2+]                                  0.020
[Pb.sup.2+]                                  0.021
[Mn.sup.2+]                                   16
[Fe.sup.2+]            Optical                11
[Cu.sup.2+]                                   12
[Fe.sup.3+]                                   50
[Hg.sup.2+]            Optical               0.233
[Hg.sup.2+]                                  0.509
[Hg.sup.2+]          Biooptical              0.602
[Ag.sup.+]                                   0.324
[Cd.sup.2+]     Optical-electronical         0.152
[Pb.sup.2+]                                  0.029
[Cd.sup.2+]                                  0.315
[Pb.sup.2+]        Electrochemical           0.292
[As.sup.3+]                                  0.172
[Hg.sup.2+]                                  0.321
[Cu.sup.2+]          Biooptical            5547.566

Analytes                  Waterbodies                Ref.

[As.sup.3+]        Tap, lake, and pond water         [203]
[As.sup.3+]               River water                [204]
[Cd.sup.2+]            Tap and lake water            [205]
[Pb.sup.2+]
[Pb.sup.2+]            Tap and lake water            [206]
[Pb.sup.2+]               River water                [207]
[Hg.sup.2+]
[Cu.sup.2+]           Tap and river water            [208]
[Fe.sup.3+]
[Ni.sup.2+]
[Cr.sup.6+]            Tap and lake water            [209]
[Cu.sup.2+]
[Al.sup.3+]
[Zn.sup.2+]
[Cd.sup.2+]               River water                [210]
[Pb.sup.2+]
[Cu.sup.2+]                Lake water                [211]
[Hg.sup.2+]
[Pb.sup.2+]               River water                [212]
[Cu.sup.2+]
[Ag.sup.+]    Tap, drinking, pond, and soil water    [213]
[Cd.sup.2+]
[Pb.sup.2+]               River water                [214]
[Cu.sup.2+]
[Hg.sup.2+]
[As.sub.3+]           Lake and well water            [215]
[Cd.sup.2+]                Lake water                [216]
[Hg.sup.2+]                Tap water                 [217]
[Pb.sup.2+]       River, lake, and wastewater        [218]
[Cd.sup.2+]
[Hg.sup.2+]               River water                [219]
[Cu.sup.2+]
[Pb.sup.2+]        River, tap, and well water        [220]
[Cr.sup.3+]
[Ag.sup.+]    Pond, tap, drinking, and soil water    [221]
[Hg.sup.2+]               River water                [222]
[Cd.sup.2+]        Tap, pond, and river water        [223]
[Ni.sup.2+]           Tap and river water            [224]
[Cu.sup.2+]
[Cd.sup.2+]               River water                [225]
[Pb.sup.2+]
[Cd.sup.2+]
[Pb.sup.2+]               River water                [226]
[Cu.sup.2+]
[Hg.sup.2+]
[Ni.sup.2+]
[Cr.sup.6+]                Lake water                [227]
[Hg.sup.2+]
[Pb.sup.2+]               River water                [228]
[Hg.sup.2+]           Tap and river water            [229]
[As.sup.3+]               Groundwater                [203]
[Hg.sup.2+]         Lake and deionized water         [230]
[Pb.sup.2+]               River water                [231]
[Cd.sup.2+]                Lake water                [232]
[Hg.sup.2+]               River water                [233]
[Cu.sup.2+]
[Pb.sup.2+]
[Cu.sup.2+]           Lake and river water           [234]
[Hg.sup.2+]
Pb                     Tap and lake water            [235]
Cd
[Cu.sup.2+]               River water                [236]
[Fe.sup.3+]
[Pb.sup.2+]                Lake water                [237]
[Hg.sup.2+]
[Cd.sup.2+]                Lake water                [238]
                        Deionized water
[Pb.sup.2+]           River and tap water            [239]
[Pb.sup.2+]               River water                [240]
[As.sup.3+]        River, tap, and wastewater        [241]
[Cd.sup.2+]
[Cd.sup.2+]
[Pb.sup.2+]               River water                [242]
[Cu.sup.2+]
[Cr.sup.3+]           River and tap water            [243]
[Pb.sup.2+]      Lake and mining effluent water      [244]
[Cd.sup.2+]            Lake and tap water            [245]
[Pb.sup.2+]
[Zn.sup.2+]
[Cd.sup.2+]           Tap and river water            [246]
[Pb.sup.2+]
[Cu.sup.2+]        River, tap, and dam water         [247]
[Cd.sup.2+]
[Pb.sup.2+]                                          [248]
[Ni.sup.2+]
[Zn.sup.2+]
[Pb.sup.2+]                Lake water                [249]
[Cu.sup.2+]
[Pb.sup.2+]        Tap, lake, and river water        [250]
[Ag.sup.+]             Tap and lake water            [251]
[Cd.sup.2+]               River water                [252]
[Pb.sup.2+]
[Pb.sup.2+]               River water                [253]
[Hg.sup.2+]
[Cu.sup.2+]           Tap and river water            [254]
[Pb.sup.2+]
[Cr.sup.3+]                Lake water                [255]
[Hg.sup.2+]
[Cd.sup.2+]
[Cu.sup.2+]                Wastewater                [256]
[Hg.sup.2+]
[Pb.sup.2+]
[Mn.sup.2+]
[Fe.sup.2+]               River water                [257]
[Cu.sup.2+]
[Fe.sup.3+]
[Hg.sup.2+]           River and tap water            [258]
[Hg.sup.2+]
[Hg.sup.2+]                Lake water                [259]
[Ag.sup.+]
[Cd.sup.2+]               River water                [260]
[Pb.sup.2+]
[Cd.sup.2+]
[Pb.sup.2+]           River and tap water            [261]
[As.sup.3+]
[Hg.sup.2+]
[Cu.sup.2+]           Pond wand tap water            [262]
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Author:Xiang, Hongyong; Cai, Qinghua; Li, Yuan; Zhang, Zhenxing; Cao, Lina; Li, Kun; Yang, Haijun
Publication:Journal of Sensors
Geographic Code:7ISRA
Date:Mar 1, 2020
Words:15940
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