Emerging pollutants in pharmaceutical and personal care product industrial effluents: Characterization and their environmental impacts Open Access

Pharmaceutical and personal care products (PPCPs), their metabolites, and environmental transformation products (TPs) pose a significant threat to the aquatic environment. Similar to pharmaceutical drugs, personal care products (PCPs) enter into water bodies through industrial effluents and domestic wastewater (Mathew & Kanmani 2020). Emerging pollutants (EPs) of pharmaceuticals, especially antibiotics, steroids, and hormones in the aquatic environment are found to be toxic, persistent, and non-biodegradable, which pose significant risks to aquatic life and human health (Al-Gheethi & Ismail 2014). Similarly, PCPs like phthalate, triclosan, bisphenols, etc., are endocrine-disrupting compounds (EDCs), which can disturb endocrine hormonal systems greatly (Afshan et al. 2020; Khalid & Abdollahi 2021). PPCP industrial effluents also carry varying concentrations of heavy metals (HMs), including Cr, Ni, Co, Cu, Cd, Pd, Ti, and As, which are highly toxic to both aquatic life and human health (Arshad et al. 2020). Biologically activated sludge process (ASP), physicochemical oxidation (chlorine), and combined physicochemical and biological methods of wastewater treatment processes are commonly used in Bangladesh (Khan & Mostafa 2011). Proper management of wastewater and sludge is mandatory in Bangladesh. However, due to the lack of proper monitoring, untreated industrial wastewater is often directly discharged into water bodies for economic benefits (Monira & Mostafa 2023). Many reports indicate that biological treatment is capable of removing only polar contaminants from the final discharged effluent. However, PPCPs include a wide range of chemicals, such as non-polar volatile organic compounds (VOCs), semi-polar, and polar compounds. Though conventional ASP is found to be the most cost-effective method to degrade and eliminate contaminants, it does not eradicate micropollutants, especially antibiotics, steroids, hormones, etc. (Amin et al. 2014; Falisse et al. 2017). Recent studies have reported the presence of PPCPs in industrial wastewater, surface water, and combined sewer overflows globally (Ryu et al. 2014). The presence of pharmaceutical products, such as sulfonamides, trimethoprim, macrolides, and penicillin, in the surface water of rivers in Bangladesh was also reported recently (Hossain et al. 2018). Various pharmaceutical drugs have been identified in the water system so far. Among them, antibiotics (ciprofloxacin), anti-inflammatories, antimicrobials (penicillin), anti-diabetics (sulfonylurea), anti-epileptics (carbamazepine), analgesics (ketoprofen, diclofenac), antihistamine drugs (ranitidine, famotidine), antiulcers, anti-anxiety/hypnotic agents (diazepam), and lipid regulators (Clofibrate) are a few examples of pharmaceutical products found in the aquatic environment (Arman et al. 2021). PCPs include phthalates, plasticizers such as bisphenol A (BPA), phthalic acid esters (PAEs), and perchlorate, which were also found in the surface water reported by several studies (Colborn et al. 1993). However, the study on EPs in the PPCPs' industrial discharged effluent is insufficient. In Bangladesh, the study of PPCP pollutants is limited to certain river surface water and according to our best knowledge, there is no research paper related to the study of PPCP EPs in the industrial discharged effluent.

The study aimed to investigate the occurrence of PPCPs discharged from a pharmaceutical wastewater treatment plant (WWTP) in Bogura City and a PCP WWTP in Tejgaon, Dhaka. It also aimed to assess the physicochemical parameters and HMs in PPCP industrial wastewater. The impacts of the discharged effluent on the environment were also investigated. Pearson correlation and PCA analyses were used to assess the correlation among the variables. Two-way ANOVA analysis was performed to investigate the seasonal variation. The study area was chosen based on the lack of available information regarding the suspected contamination of rivers by PPCPs in those areas.

The study selected a PCP industry in Tejgaon, Dhaka, the capital city of Bangladesh (23.8° N and 90.4° E), and a pharmaceutical industry in Bogura City (24.83° N and 89.37° E), the northern part of Bangladesh. The pharmaceutical industry releases its effluent into the Korotoa River in Bogura, and the PCP industry discharges into the Balu River in Dhaka.

Before subjecting to liquid chromatography coupled to mass spectrometry (LC/MS) analysis, the organic compounds contained in PCP wastewater samples were extracted using a sequential liquid–liquid extraction procedure. Five hundred mL of effluent sample was taken into a separating funnel and an equal amount of chloroform (CHCl₃) was then added to it. After shaking the mixture, the solvent layer was separated and placed into a beaker. One g of granulated anhydrous sodium sulfate (Na₂SO₄) was added to the separated mixture to eliminate moisture content and filter the mixture. The filtrate was then evaporated to dryness using a rotary evaporator at nearly 40 °C. The final concentrated volume of effluent extract was 50 μL (Zaugg et al. 2006; Kumari & Tripathi 2019).

The concentrated sample of the extracted analytes was analyzed with LC–MS (2020, Shimadzu, Japan) in the laboratory of the Bangladesh Council of Scientific and Industrial Research, Rajshahi (BCSIR), Bangladesh, according to the standard method (Ryu et al. 2014; Chidella et al. 2021). To characterize EPs, samples were first scanned by LC–MS in both positive and negative ESI modes. There was a ‘salvo’ having several high-intensity peaks alongside the base peak (BP). Therefore, each sample was again scanned in the selected ion monitoring (SIM) mode.

Temperature, pH, electrical conductivity (EC), total dissolved solids (TDS), and dissolved oxygen (DO) were recorded in situ using portable digital meters (Adwa, AD203; Adwa, AD100; Hanna, DiST2, and Lutron, DO-5509). All other physical and chemical parameters were measured according to the standard method of APHA (2005).

The collected samples were digested with concentrated nitric acid, and the concentrations of metals and metalloids were determined by using the flame atomic absorption spectrometer (SHIMADZU, AA-6800) in the central science laboratory at the University of Rajshahi, according to the standard method (APHA 2005).

The FTIR analysis of the extracted organic solid residue obtained from each sample was done using the Perkin Elmer Spectrum 100 FTIR machine in the central science laboratory, at the University of Rajshahi, according to the standard method (Kumari & Tripathi 2019). The extracted analytes were kept in the oven at 105 °C for about 5 h. A very small amount (1% of KBr taken) of the solid mass obtained was mixed with dried potassium bromide (KBr) (Merck), which was previously dried at 105 °C overnight in an oven. The mixture was finely ground using an agate mortar and pestle and the pellet was prepared using a Specac pellet press instrument. The analyses were carried out on FTIR spectrum by scanning 225–4,000 cm⁻¹.

The quality of the discharged effluent and its environmental impacts were assessed by the following four water quality indices.

Depending on the conditions, F3 (amplitude) is calculated with the help of the normalized sum of excursion (nse), which is calculated either by Equations (3) or (4).

Here, the failed test value indicates the value of the failed variable and objective indicates the standard limit of each parameter.

According to the proposed criteria of CCME-WQI, the water quality is considered excellent, good, fair, marginal, and poor for CCME = 95–100, CCME = 80–94, CCME = 65–79, CCME = 45–64, and CCME = 0–44, respectively (Uddin et al. 2021; Islam & Mostafa 2022).

The proposed criteria for RQs are as follows: RQ < 0.1 (minimum risk), 0.1 ≤ RQ < 1.0 (intermediate risk), and RQ ≥ 1.0 (high environmental risk) (Camara et al. 2021).

To assess the correlations among the variables, principal component analysis (PCA) and Pearson's correlation matrix were used. Factors or principal components (PCs) with an eigenvalue greater than 1 were extracted for PCA analysis. The first principal component (PC1) accounts for the greatest variability, which is equal to the weighted (factor loading) linear combination of the initial variables (Anju & Banerjee 2012; Zhou et al. 2020). Before performing the Pearson correlation, the statistical tests for linearity, normality, and homoscedasticity were done. The data violated the assumption of linearity; therefore, the data were transformed into Log₁₀ (Sahen et al. 2025). One-way analysis of variance (ANOVA) considers only one independent variable (factor) at a time, while two-way ANOVA examines the effect of two or more independent variables on a dependent variable. The two-way analysis also determines the interaction effect between those factors. However, for ANOVA analysis, data have to meet the assumptions of normality, homogeneity of variances, and independence of observations (Kim 2014). Before performing ANOVA, the three assumptions were tested. To test the seasonal variability, two-way ANOVA was performed taking season and parameter as two independent factors and parameter value as dependent variables. IBM SPSS Statistics software version 2022 and Origin Pro 2025 were used for calculating statistical analyses.

The descriptive results for physicochemical parameters, HMs, and EPs are presented in Tables 1–4.

Table 2

Chemical parameters of the pharmaceutical and PCP effluents

.	Season .	Concentrations (mg/L) .
Type .		Na .	K .	Ca .	Mg .	.	Cl− .	.	.
PPs	PRM	0.93	0.82	7.20	13.8	81	144	11.05	118.9
	MSN	1.13	0.77	6.70	12.4	56	131.97	5.1	105.8
	PSM	1.20	0.96	6.30	11.8	85	146	10.5	113.6
Mean		1.10	0.85	6.7	12.7	74	140.7	8.9	112.8
SD		±0.11	±0.08	±0.37	±0.83	±12.8	±6.19	±2.68	±5.38
PCPs	PRM	0.12	0.09	52.7	12.6	18.2	186	3.5	174.5
	MSN	0.11	0.10	42.3	9.8	22.6	212.3	2.7	205.6
	PSM	0.23	0.16	60.8	15.1	34.5	241.8	4.6	259.5
Mean		0.15	0.12	51.9	12.5	25.1	213.4	3.6	213.2
SD		±0.05	±0.03	±7.57	±2.16	±6.88	±22.79	±0.78	±35.11
ECR (2023)		–	–	–	–	10	600	5	–
DoE (2019)		200	12	75	35	10	600	6	400

.	Season .	Concentrations (mg/L) .
Type .		Na .	K .	Ca .	Mg .	.	Cl− .	.	.
PPs	PRM	0.93	0.82	7.20	13.8	81	144	11.05	118.9
	MSN	1.13	0.77	6.70	12.4	56	131.97	5.1	105.8
	PSM	1.20	0.96	6.30	11.8	85	146	10.5	113.6
Mean		1.10	0.85	6.7	12.7	74	140.7	8.9	112.8
SD		±0.11	±0.08	±0.37	±0.83	±12.8	±6.19	±2.68	±5.38
PCPs	PRM	0.12	0.09	52.7	12.6	18.2	186	3.5	174.5
	MSN	0.11	0.10	42.3	9.8	22.6	212.3	2.7	205.6
	PSM	0.23	0.16	60.8	15.1	34.5	241.8	4.6	259.5
Mean		0.15	0.12	51.9	12.5	25.1	213.4	3.6	213.2
SD		±0.05	±0.03	±7.57	±2.16	±6.88	±22.79	±0.78	±35.11
ECR (2023)		–	–	–	–	10	600	5	–
DoE (2019)		200	12	75	35	10	600	6	400

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This study revealed that the values of biochemical oxygen demand (BOD₅) and chemical oxygen demand (COD) for pharmaceutical effluent in two seasons were found to exceed the permissible limits set by both the Bangladesh Environmental Conservation Rules 2023 (ECR 2023) and the Department of Environment, Bangladesh 2019 (DoE 2019), while those values were above the standard limits for PCPs’ industrial effluent in all three seasons. The pH values for PCP industrial effluent in all three seasons were found to be below the permissible limit set by the ECR (2023), which was acidic in nature. The values of nitrate for both industrial effluents in all seasons exceeded the standard limits set by both the ECR (2023) and DoE (2019). However, the phosphate values for pharmaceutical effluent were found to exceed the desired limit in all three seasons. The remaining physicochemical parameters were found below the permissible limits set by both standards (Tables 1 and 2).

All effluents were colorless, having a temperature range of between 28 and 33 °C. The color of the effluent depends on the presence of suspended solids and TDS. The color of the effluent is an important parameter, since effluents with high pollution are usually colored (Bakare et al. 2009; Abdullahi et al. 2020; Amigun et al. 2021; Tunde et al. 2021). The TSS and the TDS in both pharmaceutical and PCP effluents are relatively lower than the previously reported data (Table 5). Therefore, both types of effluents were seen as colorless by the naked eye. The values of electrical conductivity (EC) for both effluents in all seasons were found to be within the permissible limits set by both the ECR (2023) and DoE (2019). The mean EC values for pharmaceutical and PCP effluent were 537 and 844.3 μS/cm, respectively, with standard deviations (SDs) of 41.4 and 70.6, respectively. These high values of SD suggested high fluctuation of the EC values over seasons. However, the mean EC value of PCP effluent was found to be 1.6 times higher than that of pharmaceuticals, which was due to the lower value of pH and higher values of Ca²⁺, Cl⁻, and (Tables 1 and 2). The TSS values for both effluents exceeded the standard limit. However, comparatively higher TSS values were found for pharmaceutical effluent (mean = 42.6 mg/L, SD = 5.4). TSS can include toxic chemicals, which cause turbidity that decreases the penetration of sunlight into the water body. As a consequence, the growth of phytoplankton is decreased, which lowers DO level (Castillo et al. 2022). The TDS values for both effluents were also found to be within the accepted limit set by both the ECR (2023) and DoE (2019). The mean TDS values for pharmaceutical and PCP effluent were 567 and 557 mg/L, respectively, with SDs of 44.9 and 91.3, respectively. These high values of SD suggested that the values of TDS fluctuate over seasons.

Table 5

Comparative study of the major physicochemical parameters and heavy metals

Parameter .	Previous study .		Present study .
	Pharmaceutical effluent .	Personal care product effluents .	Pharmaceutical effluent .	Personal care product effluents .
pH	6.09a	6,89d	6.67	5.10
EC (μS/cm)	451a	3,034.9d	537	844.30
TDS (mg/L)	336b	1,350.35d	567	557
COD (mg/L)	147. 04b	206.67d	212.1	468.3
(mg/L)	61.3b	–	74	25.10
(mg/L)	42b	–	8.90	3.60
Cr (mg/L)	0.016–0.17c	–	0.067	0.194
Pb (mg/L)	0.002a	1.173d	0.058	0.032
Cd (mg/L)	0.002b	1.173d	0.010	0.013

Parameter .	Previous study .		Present study .
	Pharmaceutical effluent .	Personal care product effluents .	Pharmaceutical effluent .	Personal care product effluents .
pH	6.09a	6,89d	6.67	5.10
EC (μS/cm)	451a	3,034.9d	537	844.30
TDS (mg/L)	336b	1,350.35d	567	557
COD (mg/L)	147. 04b	206.67d	212.1	468.3
(mg/L)	61.3b	–	74	25.10
(mg/L)	42b	–	8.90	3.60
Cr (mg/L)	0.016–0.17c	–	0.067	0.194
Pb (mg/L)	0.002a	1.173d	0.058	0.032
Cd (mg/L)	0.002b	1.173d	0.010	0.013

^aAbdullahi et al. (2020).^bBakare et al. (2009).^cTunde et al. (2021).^dTunde et al. (2021).

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The pH values for pharmaceutical effluent in all three seasons were within the standard limit, with a mean value of 6.67 and the SD of 0.3. However, the pH values for PCP effluent were below the permissible limit with a mean value of 5.1 and the SD of 0.4. The solubility of HMs increases with lowering the pH of the water bodies. Lower pH has an adverse effect on aquatic life, especially for microorganisms and fishes (Dewangan et al. 2023). The total hardness (TH) values for both effluents in all seasons were found to be within the accepted limit set by the DoE (2019). The mean TH values for pharmaceutical and PCP effluent were 345 and 388 mg/L, respectively, with an SD of 7.3 and 11.7, respectively. In most of the seasons, the DO values remained below the permissible limit set by both the ECR (2023) and DoE (2019). Lower values of DO can be explained by relatively higher values of BOD₅, COD, and TDS (Table 1). Both the BOD₅ and COD values in the monsoon season for pharmaceutical effluent were found to be below the accepted limit set by the ECR (2023), while the remaining values were found to exceed the standard limits. The mean BOD₅ values for pharmaceutical and PCP effluent were 46.8 and 249.9 mg/L, respectively, with SD of 15.8 and 32.7, respectively. The mean COD value for PCP effluent (468.3 mg/L) were found to be almost two times higher than that of the pharmaceutical effluent (215.8 mg/L) (Table 1). The LC–MS analysis suggested that the pharmaceutical effluent contained several cephalosporin antibiotics, such as amoxicillin, cefalexin, cefradine, cefuroxime, penicillin, etc., while PCP effluent contained several EDCs, such as BPA, butylparaben, benzyl butyl phthalate, octyl phenol, etc. These are extremely toxic compounds for aquatic life (Afshan et al. 2020; Fick et al. 2009).

The concentrations of nitrate in all seasons for both industrial effluents were found to exceed the accepted limits set by both the ECR (2023) and DoE (2019). However, the mean nitrate value for pharmaceutical effluent (74 mg/L) was found to be almost three times higher than that of the PCP effluent (25.1 mg/L) (Table 2). The concentrations of chloride and sulfate for both effluents in all seasons were found to be within the accepted limit. The mean concentrations of chloride and sulfate for pharmaceutical effluent were found to be 140.7 and 112.8 mg/L, respectively, with SD of 6.19 and 5.38. For PCP effluent, the mean concentrations of chloride and sulfate were found to be 213.4 and 213.2 mg/L, respectively, with SD of 22.79 and 35.11. The phosphate value for pharmaceutical effluent in all three seasons was found to exceed the permissible limits set by both the ECR (2023) and DoE (2019). However, the phosphate value for PCP effluent in all three seasons was found to be within the accepted limits. The mean phosphate values for pharmaceutical and PCP effluent were 8.9 and 3.6 mg/L, respectively, with SD of 2.68 and 0.78, respectively (Table 2). High concentrations of nitrate and phosphate in the effluent can lead to contamination of the water bodies, causing eutrophication (Anand et al. 2022). The concentrations of Na, K, Ca, and Mg for both effluents in all seasons were within the permissible limits of the DoE (2019) (Table 2). The mean concentrations of Na, K, Ca, and Mg for pharmaceutical effluent were found to be 1.10, 0.85, 6.7, and 12.7 mg/L, respectively, with SD of 0.11, 0.08, 0.37, and 0.83. For PCP effluents, the mean concentrations of Na, K, Ca, and Mg were found to be 0.15, 0.12, 51.9, and 12.5 mg/L, respectively, with SD of 0.05, 0.03, 7.57, and 2.16. Commercial limestone is used in the wastewater treatment process to increase the pH to the optimum level in PCPs WWTP, which increases the concentration of Ca and Mg. In pharmaceutical effluent, the higher value of Mg is due to the use of Mg(OH)₂ in the antacid manufacturing process.

The heavy metal concentrations were found to be within the accepted limits of the ECR (2023) guidelines. However, the mean concentrations of Cr and Cd for both effluents, the mean concentrations of Ni and Pb for pharmaceutical effluent, and the mean concentrations of Mn for PCP effluents were found to exceed the permissible limits set by the DoE (2019) guidelines (Table 3). The mean concentrations of Cr for pharmaceutical and PCP effluents were found to be 0.067 and 0.194 mg/L, respectively, with an SD of 0.01 for both effluents. The mean concentration of Mn for PCP effluents was found to be 0.232 mg/L with an SD of 0.01. For pharmaceutical effluent, the mean concentration of Ni was found to be 0.104 mg/L with an SD of 0.09. The mean concentration of Pb for pharmaceutical effluent was found to be 0.058 mg/L with an SD of 0.05. The mean Cd concentrations for pharmaceutical and PCP effluents were 0.01 and 0.013 mg/L, respectively, with SDs of 0.01 and 0.003. The continuous discharge of industrial effluent containing toxic HMs can slowly accumulate in the water bodies and consequently contaminate groundwater. Mineral pigments containing HMs such as Cr, Mn, Fe, Ni, Cu, Zn, Pd, and Cd, are commonly used in the manufacturing of cosmetics for color, skin sensitizers, and antimicrobial agents (Arshad et al. 2020). On the other hand, HMs are directly used as catalysts and reagents in the pharmaceutical manufacturing processes. HMs in pharmaceutical wastewater may also originate from the trace impurities in raw materials, and as byproducts of various chemical tests and processes (Bibi et al. 2023).

The list of EPs found by LC–MS analysis in pharmaceutical and PCP effluents is presented in Table 4. A total of 37 EPs were identified in pharmaceutical and PCP effluents; of them, 22 EPs were found in pharmaceutical effluent, including 12 compounds that are antimicrobial agents. Moreover, most of the antimicrobial agents are cephalosporin antibiotics, such as amoxicillin, cefalexin, cefradine, cefuroxime, and penicillin. Other notable drugs are anti-allergen (cetirizine, dexamethasone (DEX)), antihistamine (chloramphenicol maleate), anti-inflammatory (ibuprofen), anti-asthmatic (salbutamol), etc. (Table 4). Among the assigned EPs in PCP effluents, predominant groups are UV filters (benzophenone-2, benzophenone-3, para-amino-benzoic acid, benzyl salicylate), plasticizers (BPA, benzyl butyl phthalate), and synthetic musks (celestolide, phantolide, p-dimethoxybenzene). Some of the identified compounds in PCP effluents are insoluble in water. However, their presence in PCP effluents can be explained by their high affinity toward other organic pollutants present in effluent (‘Trojan-Horse effect’). Some of the identified compounds, such as BPA, butylparaben, benzyl butyl phthalate, octyl phenol, etc., in PCP effluents are EDCs.

The quality of the treated effluent depends on the characteristics of the influent and the performance and types of WWTPs used. Therefore, the physicochemical parameter results are expected to vary from industry to industry, since different WWTPs are used in different industries. However, a comparative study was conducted to show the similarities and dissimilarities with the previous works (Table 5). Like the present study, acidic pH with almost identical values was reported in the previous study conducted by Abdullahi et al. (2020) and Amigun et al. (2021) (Table 5). However, a slightly lower pH for PCPs was found in the present study compared to the previous study. Comparatively similar results were found for EC, TDS, COD, nitrate, and major HMs in the pharmaceutical effluents, however, phosphate concentration in the present study was found to be almost five times lower than the previous study conducted by Bakare et al. (2009). Contrarily, a significant variation was observed between the present and the previous studies for PCP effluents (Table 5). On the other hand, similar types of EPs in PPCP effluents were reported in the previous studies as shown in the present study (Desmidt et al. 2014; Arman et al. 2021).

The CCME-WQI analysis of pharmaceutical and PCP effluents in three seasons, considering all parameters, suggested that the treated water quality was poor. However, according to the HEI analysis, low to medium heavy metal pollution was observed for both effluents in different seasons. According to the HPI and RQ_MEC/PNEC analyses, both effluents in all seasons were unsafe for consumption and had high environmental risks considering HMs only (Table 6). Moreover, antibiotics found in the pharmaceutical effluents can kill microorganisms, contaminate microbial ecosystems, and develop antibiotic-resistant microorganisms. Pharmaceutical EPs in effluent are capable of increasing genome instability, altering blood cell indices, and causing pathological lesions in fish tissues (Hossen et al. 2024). PCP effluents contained a certain number of EDCs, such as BPA, parabens, phthalates, benzophenones, etc., that have significant environmental risks. The normal functioning of the endocrine systems of mammals is disrupted by EDCs, and as a consequence, cancer, birth defects, and developmental disorders in mammals are promoted. Hormonal disruption caused by EDCs develops learning disabilities, attention deficit hyperactive disorders, and deformities of body parts such as the limbs. If a pregnant mother is exposed to EDCs such as BPA and phthalates, the sexual development of her offspring could be hampered (Afshan et al. 2020). Animals exposed to low levels of EDCs showed similar effects as those in human beings. EDCs are very persistent in the environment and accumulate in animal and human tissues, thereby posing a significant threat to human and animal health (Fick et al. 2009). The concentrations of phosphate and nitrate in the treated effluents of PPCPs were found to be high. Phosphate and nitrate in surface water bodies, such as rivers, lakes, and the oceans, in a process called eutrophication, leads to algal blooms causing oxygen-starved dead zones (Desmidt et al. 2014). Nitrate and phosphate in surface water may slowly leach into the groundwater thereby contaminating drinking water sources. It is reported that nitrate contamination of drinking water increases the risk of certain cancers and impacts fetal development during pregnancy (Mathewson et al. 2020). Excess phosphate in drinking water can lead to accumulation in the body, which causes chronic kidney disease, and a reduced renal ability to excrete phosphate (Erem & Razzaque 2018). Some EPs, especially PCPs, were found in high concentration (intensity very high), which has a significant environmental risk. BPA, benzyl paraben, butylparaben, benzophenone-2, benzophenone-3, benzyl butyl phthalate, diethyl phthalate, and octyl phenol were found to have high concentrations, which are proven EDCs. Phantolide is a polycyclic synthetic musk fragrance, which was also found in high concentrations. Various researches revealed that exposure to certain synthetic musks like phantolide led to thyroid hormone disruption and behavioral changes in the fish, even at low concentrations. Another compound found in high concentrations was p-dimethoxybenzene, which is assumed to be toxic to aquatic and terrestrial organisms. Piperonyl butoxide has moderate impacts on the environment and poses a significant threat to aquatic life, especially in fishes and invertebrates. Its high concentration in aquatic systems may further increase the risk level. Para-amino-benzoic acid has the potential to harm aquatic life, can increase photosensitivity in organisms, and can contribute to DNA damage when exposed to UV radiation. Potential bioaccumulation and endocrine disruption in some studies on animals was found when it is released into water bodies through wastewater discharge from PCPs (Arman et al. 2021; Studzinski et al. 2021). Out of 22 EPs found in pharmaceutical effluent, 12 compounds are antimicrobial agents. Antibiotics in high concentrations cause harmful effects on the environment in three ways. Firstly, the antibiotics present in wastewater kill microorganisms by damaging the metabolic activities or inducing toxicity. Those microorganisms help impair the waste in the treatment process. Secondly, antibiotics contaminate microbial ecosystems. Thirdly, antibiotics present in such a wide range in the environment lead to the development of antibiotic-resistant microorganisms (Fick et al. 2009). Atropine is an alkaloid, which is used as an antimuscarinic agent. Though available environmental toxicity data is not sufficient, the risk of environmental impact of atropine cannot be ignored (Amiri et al. 2017). Cetirizine is an antihistamine frequently found in surface water and groundwater, which has significant environmental impacts (Almeida et al. 2017). DEX is a corticosteroid drug that is used to treat the inflammation of the skin, joints, lungs, and other organs. It belongs to a class of steroid hormones that is considered an endocrine disruptor (EDC). EDCs can disturb endocrine hormonal systems greatly (Thambirajah et al. 2021).

Pearson correlation matrix and PCA were used to investigate the correlations between variables and the factors or variables that have the greatest contribution to pollution. Seasonal variability was tested using two-way ANOVA analysis.

Pearson correlation analysis was performed to investigate the degree of interrelationships between the major physicochemical parameters (Shil et al. 2019). A very strong negative correlation was found between pH and EC (−0.914) at a significant level of 0.05, suggesting that the acidic effluent mainly contributed to increasing the EC values (Tables 1 and 7). The relationship between pH and EC may be positive or negative depending on the value of pH, more specifically the acidic or alkaline nature of the water medium. For an acidic medium (pH < 7), the lowering of pH will increase the number of protons, which will increase the EC value. However, for an alkaline medium, the raising of pH will increase the number of hydroxide ions (OH⁻), which will increase the EC value (Pujar et al. 2020). A very strong linear relationship was also found between pH and BOD₅ (−0. 926) as well as pH and COD (−0. 921) at a significant level of 0.01, suggesting that the organic compound removal efficiency of the WWTPs was highly dependent on pH. Both the pharmaceuticals and PCP industries use biological WWTPs. The average pH values of the treated effluents discharged by the pharmaceutical and PCP industries were found to be 6.67 and 5.10, respectively (Table 1). The pH value for both types of wastewater was acidic, however, the pH of the PCPs wastewater was too acidic for microorganisms to survive (Jin & Kirk 2018). Therefore, very strong negative linear relationships were found between pH and BOD₅ and pH and COD. A moderate negative correlation was found between EC and DO and a weak negative relationship between TSS and DO, while a very strong negative linear relationship was found between TDS and DO (−0. 726). These types of relationships between EC and DO, TSS and DO, and TDS and DO are natural and are found in almost all water quality analyses (Kabir et al. 2020). However, a positive relationship between DO and TDS was also reported (Panda et al. 2018).

The PC1 is also strongly negatively correlated with pH, TSS, TH, Na⁺, K⁺, ⁠, PO₄³⁻, and Fe. However, the PC2 is strongly positively correlated with Ni, Pb, and Cd. For PC2, a strong negative correlation was also found with DO. For PC3, a strong positive correlation was observed with Mg, while a strong negative correlation was also found with temperature (Table 8).

The study results showed that the pharmaceutical effluents were slightly acidic (6.3–6.9), while PCP effluents were moderately acidic (4.5–5.5) in all three seasons. For PCP effluents, the values of BOD₅ and COD for all three seasons were found to be very high above the accepted limits set by the ECR (2023), while for pharmaceutical effluent, these values were slightly exceeded for two seasons. For both types of effluents, the concentrations of nitrate (⁠⁠) in all three seasons were found to exceed the standard limits. However, the concentrations of phosphate (⁠⁠) for pharmaceutical effluent in all seasons were above the permissible limits set by the ECR (2023). For pharmaceutical effluents, the mean heavy metal concentrations were in the order of Fe(0.57) > Ni(0.104) > Cr(0.067) > Mn(0.054) > Pb(0.05) > Zn(0.044) > Cu(0.0222) > Cd(0.01), while for PCP effluents, the order was Cu(0.314) > Mn(0.232) > Cr(0.194) > Fe(0.187) > Zn(0.032) ≥ Pb(0.032) > Ni(0.026) > Cd(0.013). The mean concentrations of Ni and Pb for pharmaceutical effluent, Mn for PCP effluents, and Cr and Cd for both types of effluent were above the accepted limits set by the DoE (2019). The study showed that the pharmaceutical effluent contained several cephalosporin antibiotics, such as amoxicillin, cefalexin, cefradine, cefuroxime, penicillin, etc., along with some other types of harmful drugs. However, their intensities were found to be very low, indicating a very trace amount of EPs are released into the aquatic system. The study also revealed that PCP effluents contained several EDCs, such as BPA, butylparaben, benzyl butyl phthalate, octyl phenol, etc. The intensities of EPs for PCPs were found to be very high, suggesting that comparatively higher amounts of organic compounds are discharged by PCPs industry. The CCME-WQI, HPI, HEI, and RQs suggested that both types of effluent were poor in quality and unsafe for consumption, which had high environmental risk. Pearson correlation matrix and PCA suggested that pH, EC, BOD₅, COD, ⁠, PO₄³⁻, and were the most correlating and contributing factors. Overall, the water quality of the pharmaceutical effluent was better as compared to that of PCP effluents. The ANOVA analysis results illustrated that there was no statistically significant seasonal variation observed, indicating the WWTPs of pharmaceutical and PCP industries equally performed over the year. A total of 37 EPs, including antibiotics and EDCs, were identified in both the treated effluents, which are very toxic to aquatic life and the environment. Hence, advanced treatment processes (combined treatment plant consisting of biological, oxidation, and adsorption) should be implemented to improve the discharged effluent quality.

The authors would like to thank the authorities of the studied pharmaceutical and personal care products industries for their cooperation in carrying out this research. We would also like to show gratitude to the authorities of BCSIR and the Central Science Laboratory of Rajshahi University.

All relevant data are included in the paper or its Supplementary Information.

The authors declare there is no conflict.