Water Quality analysis
Six parameters of physicochemical properties in paddy water samples were identified including pH, temperature, turbidity, BOD, COD and TSS as shown in Table 1. The pH value of paddy water was 6.5, which is equivalent to what has been found for other rice fields in northern Malaysia. According to Aqmal-Naser & Ahmad (2018), the reasons that may affect the pH water are rainfall distribution, application of fertilizer and also decomposition of organic material like weeds and rice stalks.
Table 1
Water quality of paddy water sample
pH
|
Temp (°C)
|
Turbidity (NTU)
|
BOD (mg/L)
|
COD (mg/L)
|
TSS (mg/L)
|
6.5
|
33.8
|
23.7
|
6
|
109.2
|
17.3
|
The BOD and COD concentrations are 6 mg/L and 109.2 mg/L, respectively. BOD and COD values reflect the quantity of dissolved oxygen required for microbes and chemicals to breakdown organic substances. As indicated by Suratman et al. (2015) and Wu et al. (2018), concentrations of BOD and COD will remain high in the presence of significant organic contamination in the environment. This could be because paddy water has a high content of organic materials, including crop waste, fertiliser discharge feces, and other wastes, as bacteria use more oxygen by microorganisms to break down the organic material during the oxidation process. Total suspended solid is one of the crucial indicators used to assess water quality since it defines residential wastewater concentration and influences water turbidity. Paddy water sample shows a low concentration of TSS; 17.3 mg/L was recorded. This was due to seawater dilution as the sample was near an estuary (Kamarudina et al. 2020).
Degradation of carbofuran in paddy water samples.
The presence of carbofuran and its transformation products in the water will be monitored in 56 days, and samples will be stored under two conditions (with and without sunlight). Samples were taken and extracted as the concentrations of the samples were measured with external standard solutions. It was observed that the degradation of carbofuran in the first 28 days was more compared 28 to 56 days throughout the experiment. Figure 3 illustrates the declining concentration of carbofuran in paddy water, implying that carbofuran rapidly disappeared in the first week and, in general, continue declined slowly until day 56.
The intermediates were also reviewed in order to have full understanding of major degradation mechanism involved in the carbofuran photodegradation. Only two carbofuran by-products were found using GC-ECD analysis by comparing to genuine analytical standards. Started at day 7, both 3-ketocarbofuran and carbofuran–phenol was detected as metabolites and their concentrations increased even with low levels of concentration, range in 0.03 to 0.23 ppm. From previous study by Siddaramappa et al. (1978), carbofuran was rapidly hydrolysed to carbofuran phenol in just five days after its application to paddy water. The turbidity of the sample began to decrease during monitoring, which may have led to a faster rate of carbofuran breakdown in the first half period. With fewer suspended solids in the solution, sunlight may permeate the solution more efficiently, allowing photo-degradation to occur more rapidly. There is no evidence of algae growth throughout the experiment because of the nutrient deficiency in the sample.
Figure 4 showed the carbofuran degradation trend in the water without sunlight. The carbofuran degradation was slower when stored in the dark than when exposed to sunlight, as seen in the figure. According to the findings, degradation began on day 1 and persisted until day 56. The degradation of carbofuran showed similar trend when exposed to sunlight or not. However, at day 56 of experiment, carbofuran concentration in the dark still quite higher, 0.32 ppm compared to in the light, 0.03 ppm.
As shown in Figs. 3 and 4, carbofuran degradation decreased similarly for both conditions; either when exposed to sunlight or when kept in the dark. In paddy water, carbofuran is degraded by hydrolysis and oxidation. However, only small amounts of 3-ketocarbofuran and carbofuran-phenol were detected simultaneously in the water extract. 3-ketocarbofuran reached a maximal concentration after day 35 and was subsequently stable, whereas there was a slow increase in concentration for carbofuran phenol between days 28 to 56.
From Table 2, it was found that most of the carbofuran exposed to the sunlight was degraded from its initial concentration, 93.62%, compared to kept in the dark, the percentage of carbofuran degradation was only 67.01% in the paddy water at the end of the experiment. Carbofuran may take more time to degrade when only hydrolysis and oxidation as the main degradation pathways that occur through the process. While 3-ketocarbofuran and carbofuran-phenol were detected throughout the experiment, their concentrations were widely diverse.
Table 2 Percentage (%) of carbofuran degradation and its metabolites occurrence in paddy water sample
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)
In summary, in this study that carbofuran degrades faster in the first week. Similarly reported by Ecobichon (2019) and Knaak (1971), carbofuran was extremely degraded within one week. Furthermore, the rate of loss of carbofuran kept in the dark was a little bit slower than when the water exposed to sunlight. Many pesticides are altered by 'oxidizers generated by sunlight' rather than directly absorbing sunlight (Field 2013). Besides, the same conditions applied when it was kept in dark, but it degraded faster with the presence of sunlight. Carbofuran is a water-insoluble compound that can accumulate over time, so many countries have prohibited its usage (Lan et al. 2020).
Figure 5 below showed mechanism reaction pathways of carbofuran (direct photodegradation) in the water samples that were exposed to sunlight and its metabolites, carbofuran–phenol and 3-ketocarbofuran that were formed when the water was exposed to sunlight. Carbofuran is mostly metabolised in water by hydrolysis and photolysis.
Carbofuran is degraded by direct sunlight and several photoproducts have been discovered by (Howard et al. 2017; Remucal 2014). The pesticide's photodegradation rate is substantially faster in seawater, pond water, and humic acid solutions than in distilled water at the same pH values, implying that dissolved organic matter is indirectly sensitized in photodegradation, a critical loss mechanism. While carbofuran degrades more rapidly in river water than seawater, the addition of humic acids has been shown to lower the direct photolysis rate of carbofuran (Atwan et al. 2020; Campbell et al. 2004; Iwafune 2018).
According to Zacharia (2011), insecticides are commonly applied to manage broad variety of insects and have a lengthy residual effect in the environment due to their resistance to most chemical and microbiological degradation (Gaur et al. 2018). Carbofuran degradation was connected with the development of carbofuran-phenol, the carbofuran hydrolysis product, and its formation in paddy water, which can also be proven by thin-layer chromatography (Mudhoo et al. 2019; Parte et al. 2017; James N Seiber and Cahill 2022). There have been some forensic studies on carbofuran toxicity, especially with samples that have been exposed to the sun. The analysis of its by-products is essential, because they seem to last longer and even be more prevalent than the parent pesticides. This is especially important in tropical environments, where carbofuran breakdown from the application site can be relatively fast (Lalah et al. 2001; Otieno et al. 2010).
Determination of rate of degradation, k and half-life of carbofuran
According to Farahani et al. (2012), chemical degradation can be defined by a first-order degradation curve (\(\complement ={\complement }_{o}{e}^{-kt}\)) or (\(ln\complement =ln{ \complement }_{o}-kt\)) where C is the compound's concentration at time t, C0 is the compound's initial concentration, and k is the rate constant. A pesticide's half-life is described as the time it takes for the pesticide concentration to be half that of its initial concentration, as defined by t1/2 = ln 2/k. A straight line may be formed by plotting the ln of concentration vs. time from which the rate constant (k) and half-life (t1/2) can be calculated. List of degradation rate and different half-life of carbofuran insecticide when exposed to sunlight and kept in the dark from previous study are presented in Table 3.
Table 3
Rate constant of degradation (k) and half-life (t1/2) of carbofuran in paddy water samples exposed to sunlight and kept in dark
Compounds
|
This study
|
Farahani et al., 2012
|
Cromlab, 2010
|
Kim & Kim, 2002
|
Seiber et al., 1978(Campbell et al. 2004)
|
Rate constant (day − 1)
|
Half-life (day)
|
Half-life (day)
|
Half-life (day)
|
Half-life (day)
|
Half-life (day)
|
Carbofuran exposed to sunlight
|
0.040
|
17.33
|
6.6
|
6.25
|
9.7
|
7.2
|
Carbofuran kept in the dark
|
0.0186
|
37.27
|
8.6
|
-
|
-
|
9.3
|
Table 3 showed that the half-life of carbofuran for this study was double that of most previous studies. This happened due to pH of paddy water was acidic compared to other studies, which were higher and more alkaline. Carbofuran's ability to remain stable in water gradually decreases as the pH of the water increases (Howard et al. 2017; Khan et al. 2020). Paddy water pH changes during the day in rice fields because of photosynthesis and respiration by algae. It can vary from pH 7 at 0700 h to pH 9 at 2100 h (Choudhury and Kennedy 2005). Early in the growing season, this pattern is more prominent before the canopy blocks sunlight from reaching the paddy water. Additionally, colloidal matter in paddy soils may absorb ultraviolet light, drastically lowering the energy available for photodegradation. At this time of year, carbofuran is sprayed on paddy fields. It shows that the fast dissipation seen in rice paddies is caused by hydrolysis at high pH (Katagi 2016).
The photolysis may help in enhancing the degradation process in the water. UV radiation from the sunlight which makes up around 10% of the Sun's overall electromagnetic radiation output, can break specific chemical bonds, creating transformation products. Bachman and Patterson (1999) developed a pathway for the UV degradation of carbofuran that involves the Fries' rearrangement, which produces a by-product that is consistent with the hydrolysis of the ethereal moiety of the 2,3-dihydro furan ring. It was found that when carbofuran was exposed to sunlight, the rate at which it degraded was faster than when it was kept in the dark.
It was concluded that the water sample exposed to sunlight had a faster rate of degradation of carbofuran than the water sample that was not exposed to sunlight., 0.04 day-1 with correlation coefficient R2 = 0.8758 compared to the water, which was kept in the dark 0.0186 day-1 with a correlation coefficient R2 = 0.9771. Half-life, t1/2 calculated for carbofuran is 17.33 days when exposed to sunlight, meanwhile 37.27 days when kept in the dark. According to Goldsborough & Brown (1993), the half-life of glyphosate in water is 10.0 days, less than carbofuran, indicating that carbofuran is more stable in water than glyphosate (Maqueda et al. 2017).
The carbofuran half-life in the environment is approximately 30–120 days, based on the pesticide, its location, temperature, soil or water pH, and the surrounding medium's moisture content. The major routes of carbofuran degradation are hydrolysis in basic surroundings, exposure to sunlight, and biodegradation activities (Cid-Samamed 2018; Vishnuganth et al. 2017). Carbofuran is relatively soluble in water and highly mobile in soils compared to other insecticides. This can affect water pollution control (Chae and An 2018). As shorter half-life residue was at a lower temperature (25ºC) than in a higher temperature, it was found that these pesticides were faster degrade in the water sample (Matthies and Beulke 2017). The presence of ions, organic molecules, and chemical sensitizers may have facilitated carbamate pesticide photodegradation. Previous study by Detomaso et al. (2005) stated that carbofuran phenol, 3-hydroxycarbofuran and 3-keto carbofuran were found in photodegradation experiments. Carbofuran exhibited excellent stability in water when exposed to sunshine, and its half-life was significantly shorter when exposed to sunlight than in the dark. The prolonged half-life observed when kept in the dark is almost certainly due to the absence of sunshine (Kaur et al. 2021; Remucal 2014).
The pesticides transformed by ‘oxidizers formed by sunlight as many of pesticides do not absorb sunlight directly. Photochemical breakdown, as a rule the breakdown is not complete and leads to the formation of breakdown products (Peña et al. 2020). This is why many countries have prohibited its use due to its persistence in water and its transformation into other products, which allowed it to remain in the water longer. This discovery demonstrated that sunlight can enhance carbofuran degradation in water and that photodegradation and hydrolysis are the main routes for carbofuran degradation in water.
There have been few researches on identifying and routinely analysing their major degradation products, that can be just as lasting and toxic as their parent substances (Nollet and Rathore 2016). According to earlier findings by Daramola et al. (2015) and Ramasubramanian & Paramasivam (2018), carbofuran and 3-hydroxy carbofuran are the most stable carbofuran metabolites. Because the former is more toxic than carbofuran, it poses a significant risk to people, although the 3-hydroxy carbofuran may still cause severe consequences.