Ecotoxicology and Environmental Safety 183 (2019) 109497

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Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Occurrence and health risk assessment of pharmaceutical and personal care T

products (PPCPs) in tap water of Shanghai
Min Liua,*, Haowen Yina, Qiang Wub,**
a
Bioassay and Safety Assessment Laboratory, Shanghai Academy of Public Measurement, 201203, Shanghai, China
b
Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, College of Environmental and Chemical Engineering, Shanghai University of
Electric Power, Shanghai, 200090, Shanghai, China

ARTICLE INFO ABSTRACT

Keywords: A monitoring study of 71 pharmaceuticals and personal care products (PPCPs) in tap water covered all districts
PPCPs of Shanghai. Nineteen PPCPs were detected in all samples, and most of them were detected with high con-
Tap water centration. Ten compounds were found with highest concentrations and their detection frequencies were over
Phenicols and chatain drugs 80%, included thiamphenicol (101.54 ng/L), florfenicol (84.56 ng/L), valsartan (66.84 ng/L), irbesartan (38.35
Distribution characteristics
ng/L) hydrochlorothiazide (33.13 ng/L), 4-acetaminopyrine (48.16 ng/L), propylparaben (47.50 ng/L), dicy-
Human health risk assessment
clohexylamine (42.33 ng/L), primidone (32.85 ng/L) and bisphenol A (31.51 ng/L). Only 6 PPCPs were not
detected in all samples. Detection frequency of PPCPs was between 50% and 70% in most tap waters, but the
total concentration of PPCPs ranged from 71.6 to 361 ng/L. Phenicols was the dominant type with average value
of 100 ng/L, accounting for over 50% of most samples, followed by cardiovascular and psychotropic drugs with
average value of 26.3 and 12.1 ng/L, respectively. In general, the residues of PPCPs in tap water of suburb were
higher than those in central districts. The maximum residues happened in D district with the average con-
centration of 355 ng/L, followed by J, H and Cb districts with the average concentration of 269, 251 and 215 ng/
L. In the same district, the content and distribution of PPCPs in tap waters were similar supplied by different
water treatment plants. While those are some differences among tap waters inlet from the same water sources.
Individual compound was expected to pose a negligible risk to human health with risk quotients (RQ) less than 1,
except primidone which may pose potential risk to infants.

1. Introduction Water source was no exception. Chang et al. analyzed the antibiotics in
Three Gorge Reservoir in Chongqing region of China, and found that 10
Pharmaceuticals and personal care products (PPCPs) have been of 42 antibiotic compounds were detected in source water (Chang et al.,
detected as emerging contaminants in the aquatic environment ubi- 2010). Conventional water treatment processes, however, were con-
quitously. Many types of PPCPs have been detected at low concentra- firmed to be ineffective method to remove PPCPs. Qiao et al. (2011)
tions (usually ng/L) in surface and tap water sources around the world found 15 PPCPs at concentrations of 0–36 ng/L in source water and 12
(Padhye et al., 2014; Li et al., 2018). PPCPs are biologically active in PPCPs at concentrations of 0–20 ng/L in treated water, respectively.
humans and animals (Boxall et al., 2012); they may be exerted actively The occurrence of drugs in tap water sources and limited treated
at low concentrations (Vulliet and Cren-Olivé, 2011), and potentially capacity of water treatment processes, which has raised concerns about
impacted tap water quality (Jones et al., 2005). Adverse effects were the safety of tap water (Qiao et al., 2011; Lin et al., 2016; Yang et al.,
caused by PPCPs including aquatic toxicity, antibiotic resistance and 2017). Recently, some studies found that the hot spots for PPCPs pol-
endocrine disruptions on humans, livestock and aquatic life (Jiang lution were those river waters affected by megacities with high density
et al., 2013; Li et al., 2018). Therefore, PPCPs was considered as a of population, such as Beijing, Tianjin, Guangzhou and Shanghai (Bu
potential threat to the ecosystem and human health. et al., 2013). Leung et al. also found that cities within the Yangtze River
In China, human and veterinary pharmaceuticals have been fre- region were the hot spots because of frequent positive detections and
quently detected in wastewater and surface waters (Sun et al., 2015). elevated pharmaceutical levels (Leung et al., 2013).

*
Corresponding author.
**
Corresponding author. .
E-mail addresses: [email protected] (M. Liu), [email protected] (H. Yin), [email protected] (Q. Wu).

https://doi.org/10.1016/j.ecoenv.2019.109497
Received 2 April 2019; Received in revised form 17 July 2019; Accepted 29 July 2019
Available online 07 August 2019
0147-6513/ © 2019 Published by Elsevier Inc.
M. Liu, et al. Ecotoxicology and Environmental Safety 183 (2019) 109497

Shanghai is located in the Yangtze delta, one of the most developed extraction. Before extraction, all the water samples were vacuum fil-
cities in China. A population of 25 million has been relied on Huangpu tered through 0.22 μm glass fiber filters (GF/F, Whatman) and then
and Yangtze Rivers for water supply. With the rapid modernization of spiked with corresponding internal standard solutions. The detail pro-
city, it may be faced with much threat of contaminants. Wen et al. in- cess of sample preparation and analysis was shown in Text S1 and Table
vestigated 5 pharmaceuticals in Huangpu River system over a period of S1.
almost two years, and found their ubiquitous presence in water (Wen
et al., 2014). Besides, 15 psychiatric pharmaceuticals, such as alpra- 2.5. Quality control
zolam, diazepam, were also detected in 5 tap water of Shanghai along
Huangpu River (Wu et al., 2015). These studies were limited due to few Linear internal standard calibration curves were plotted depending
targeted compounds and limited regions. Up to now, there is short of a on the sensitivity of each analyte. Limit of detection (LOD) and the limit
comprehensive investigation on PPCPs in the tap water in the whole of of quantification (LOQ) for each analyte was defined as the con-
Shanghai. Tap water is supplied by different water sources and water centrations corresponding to the signal-to-noise (S/N) ratios of 3 and
treatment plants, which would affect the residues level of PPCPs. 10, respectively. LOD and LOQ of the PPCPs in sample were 0.5 pg/L-
Therefore, it's necessary to comprehensively investigate the content and 0.1 ng/L and 1.00 pg/L-0.50 ng/L, respectively, as shown in Table S2.
distribution characteristics of PPCPs in all districts of Shanghai. To determine the accuracy and repeatability of the method, dupli-
The objectives of this investigation were to: (i) analyze PPCPs in tap cated samples were analyzed, and spiked sample was added to each 20
water as much as possible from all water treatment plants in Shanghai; samples during the analysis. In addition, the standard calibration curve
(ii) characterize PPCPs in tap water supplied by different water treat- was plotted each time. The average recoveries of the PPCPs were be-
ment plants and water sources, and (iii) evaluate the human health risk. tween 80.5% and 141% for all PPCPs, as shown in Table S2.
This work will provide important information about water quality and
its influence factors, which would help to design the targeted super- 2.6. Statistical analysis
vision on water supplies.
SPSS 21.0 software (IBM Corporation, USA) was applied for statis-
2. Materials and methods tical analysis. A Student-Newman-Keuls analysis and clustering analysis
were applied.
2.1. Chemicals and materials
2.7. Risk of human health
Seventy-one target compounds were categorized into different
groups, including antibiotics (sulfonamides, quinolones, phenicols and A screening-level assessment of the human health risks was per-
others), other veterinary drugs (fungicide, β-agonist, insecticide), car- formed based on risk quotients (RQs) for different life stages to increase
diovascular drugs (antihypertensive drugs, lipid regulating agents, β- the accuracy of risk assessment. Life stages selected were based on those
blockers), psychotropic drugs, analgesic/anti-inflammatory drugs, pre- recommended by handbook “Highlights of the Chinese exposure factors
servatives, anti-demal allergy, enzyme inhibitor and others. handbook (Child)” and “Exposure factors handbook of Chinese popu-
PPCPs and selected internal standards were obtained from Sigma- lation (adult)” in Table S3 (Duan, 2016; EPA, 2013). RQs were esti-
Aldrich (Steinheim, Germany), J&K scientific (Beijing, China) and mated for PPCPs by the method that the maximum concentration found
Altascientific (Tianjing, China). in the samples for each PPCPs divided by a respective drinking water
Methanol (LC grade), and other reagents were purchased from equivalent level (DWEL) related to different age-intervals (Equation
Sigma-Aldrich (Steinheim, Germany). Water was purified by Milli-Q (1)). For estimation of the DWELs, Equation (2) was applied.
(Millipore, MA, USA). Single stock solutions with a concentration of
1000 mg/L of each PPCPs compound and selected internal standards Cs
RQ =
were prepared in methanol. Standard mixture was prepared by diluting DWEL (1)
the stock solutions with methanol. All standard solutions were stored at (ADI × BW × HQ)
4 °C. DWEL =
(DWI × AB × FOE) (2)

2.2. Instruments ADI is the acceptable daily intake (μg/kg day); BW represents the
50th percentile values of body weight; HQ is the hazard quotient, which
An automatic solid phase extraction system (Dionex, Autotrace 280, was assumed to be 1; DWI is the tap water intake (L/day); AB represents
USA), a nitrogen-blowing instrument (Organomation, Multivap™ 6116, the gastrointestinal absorption rate, which was assumed to be 1; and
USA), and an ultra-high-performance liquid chromatography tandem FOE is the frequency of exposure (350 days/365 days = 0.96) (Gaffney
mass spectrometry system (UPLC-MS/MS) (Waters, Acquity™/Xevo TQ- et al., 2015).
XS, USA) were used in this study. In this study, ADIs were preferred in the regulations. Then those
values were adopted in literatures. When several ADI values were found
2.3. Sampling collection in the literatures, the minimum value was selected. Maximum detected
concentrations were used to provide a conservative “worst-case” sce-
Thirty-five water samples were collected in Jan-Feb, 2018, 5–6 L nario.
each, and collected in brown glass bottles from residential districts near
to water treatment plant to ensure tap water supplied by the corre- 3. Results and discussion
sponding plant. The samples were collected from all districts (15 dis-
tricts) covering all water supply companies (10 companies) and 35 3.1. The occurrence of PPCPs in tap water
water treatment plants in Shanghai. The sample collection diagram was
shown in Fig. S1. Water samples were stored in a 4 °C cool room and Table 1 shows the detection frequency and maximum value, median
extracted within 48 h after collection. value and mean of PPCPs with detected concentration higher than 1 ng/
L or 100% detected PPCPs. There were 19 PPCPs with the detection
2.4. Sample preparation and analysis frequency of 100%, accounting for 25% of the total PPCPs. Only 22.4%
PPCPs were detected with detection frequency less than 20%. And only
The targeted PPCPs were extracted and concentrated by solid phase 6 PPCPs were not detected in all samples, including sarafloxacin,

2
M. Liu, et al. Ecotoxicology and Environmental Safety 183 (2019) 109497

Table 1
Frequencies (100%) or concentration (Max. > 1 ng/L) of PPCPs in tap water and references values (ng/L).
Compounds Frequency (%) Max. Mean Median references

Frequency (%) concentration

a
Thiamphenicol 100 101.54 49.3 37.08 75 7 a, 104b
Florfenicol 100 84.56 42.04 32.03 – –
Valsartan 82.9 66.84 9.57 2.99 – ndc,d
4-acetylamino- antipyrine 91.4 48.16 7.78 0.19 15s,e 1.6s,e, nds, f, g
Propyl paraben 100 47.5 5.27 3.3 62.5a 9a
Dicyclohexylamine 100 42.33 9.76 9.04 – –
Irbesartan 100 38.35 8.1 7.22 – ndc
Hydrochlorthiazide 100 33.13 7.16 1.62 – 7c
Primidone 100 32.85 8.86 6.26 – ndc
Bisphenol A 100 31.51 2.91 0.78 25a, 17h, 12j 6a, 220h, nqi, 99j
Sulfadiazine 100 17.48 2.04 0.22 – ndh
Aspartame 80 10.16 4.14 3.56 – –
Carbamazepine 100 9.70 1.75 1.31 13e, 13k,j, 110h, 25j, 55d 0.65e, ndf, 25k,140h, 601j, 588d, 2.5l
Methyltestosterone 100 9.57 1.4 0.82 – ndt,d, 41.6t,m
Sulfamethoxazole 54.3 9.57 1.28 0.02 80e, 25f, 13k, 0h, 1i,j, 11d 5.4e, 0.5f, 3n, 12.7k,j, 0.23g, ndh,o, 2i,j, 8.2d, 11m, 21.2b
Chloroamphenicol 100 6.60 2.23 1.86 12.5a 2a
Marbofloxacin 22.9 4.04 0.45 nd – –
Nalidixic acid 94.3 3.87 0.41 0.23 – –
Sulpiride 94.3 3.61 0.86 0.24 25e,75f 1.7e, 0.17f, 0.18g,
Losartan 68.6 3.25 0.6 0.39 – ndc
Sulfamethazine 68.6 3.20 0.36 0.03 – ndo, 89.6b
Ciprofloxacin 28.6 2.76 0.21 nd – 212p
Tetramisole 85.7 2.33 0.27 0.05 – –
Phenytoin 100 1.93 0.59 0.33 – –
Diphenhydramine 100 1.7 0.42 0.33 – ndd,h
Praziquantel 100 1.55 0.53 0.46 – –
Clofibric acid 100 1.55 0.41 0.17 62.5a, 1j 19a, 5.5u,q, ndi
Clorprenaline 100 1.4 0.31 0.06 – –
Trimethoprim 94.3 1.35 0.43 0.21 35e, 88k, 1j 3.7e, ndd,f,o, 1.4m, 19.8k, 15j
Sulfapyridine 82.9 1.27 0.19 0.02 – –
Clindamycin 100.0 0.76 0.13 0.09 – –
Thiabendazole 100.0 0.70 0.18 0.13 – –

a
Spain (Carmona et al., 2014).
b
Yangtze River and Pearl River (Leung et al., 2013).
c
Spain (Maria et al., 2011).
d
U.S.(Furlong et al., 2017).
e
Taihu (Lin et al., 2016).
f
Southern China (Yu et al., 2010).
g
China (Yu et al., 2010).
h
U.S. (Stackelberg et al., 2007).
i
U.S. and Canada (Boyd et al., 2003).
j
Canada (Kleywegt et al., 2011).
k
U.S. (Padhye et al., 2014).
l
Shanghai (Wu et al., 2015).
m
France (Vulliet et al., 2011).
n
Taiwan (Yang et al., 2014).
o
Chongqing (Yan et al., 2014).
p
Guangzhou (Wang et al., 2009).
q
Shanghai (Wen et al., 2014).
s
The value is the concentration of antipyrine.
t
The value is the concentration of testosterone.
u
Huangpu river water source.

lincomycin, meroxicam, zearalenon, warfarin and dienestrol. As shown 26.3 ng/L, accounting for 58% and 15% of total PPCPs, respectively.
in Table 1, an analyte, whose maximum detected concentration was Secondly, psychotropic drug, enzyme inhibitor and anti-inflammatory
greater than 1 ng/L, also had high detection frequencies over 50% with drugs accounted for 7%, 6% and 5% of the total PPCPs. Others types of
a few exceptions. Moreover, those PPCPs, whose maximum con- PPCPs accounted for less than 2% such as other veterinary drugs,
centrations were all greater than 1 ng/L, had detection frequencies of steroids and anti-demal allergyic agent. It was surprised that phenicols
100%, except for thiabendazole and clindamycin. As expected, among accounted for 94% of the total antibiotics, and the average concentra-
the top 10 PPCPs with highest concentrations, thiamphenicol, florfe- tion of florfenicol and thiamphenicol reached 84.56 and 101.54 ng/L.
nicol, dicyclohexylamine, ibesartan, primidone had high median value, This was probably due to that chloramphenicol had been prohibited to
which showed that most samples contained them with high con- be used in animal foodstuff by regulation, while florfenicol and
centration. While other antibiotics had low median values, indicating thiamphenicol were just restricted with residue limits of 100–2000 μg/
their uneven distribution. kg and 50 μg/kg, respectively (Announcement of the Ministry of
The distribution of various types of PPCPs is shown in Fig. 1. It Agriculture, No. 235, 2002). Florfenicol and thiamphenicol had been
could be seen that antibiotics and cardiovascular drugs were the most increasingly applied as the alternatives of chloramphenicol so that their
dominant compounds with the average concentration of 100 and levels were far higher than that of chloramphenicol. It was reported

3
M. Liu, et al. Ecotoxicology and Environmental Safety 183 (2019) 109497

Fig. 1. Composition of all types of PPCPs.

that the used amount of florfenicol ranked among the top 5 veterinary et al., 2014; Yu et al., 2010), but it was higher than that in American
drugs (Feng et al., 2017). Sulfanilamide and quinolone only counted for (Vulliet et al., 2011) and Canada (Boyd et al., 2003). The characteristic
4% and 1% with average concentration of 4.01 and 1.37 ng/L. Among of trimethoprim was similar to sulfamethoxazole as shown in Table 1.
11 sulfanilamide, sulfadiazine, sulfamethazine and sulfamethoxazole With one exception, the concentrations of sulfamethoxazole and tri-
had relatively high detection frequency (54.3%–100%) their maximum methoprim reached 12.7 and 19.8 ng/L in the southern United States
concentration (3.20-17.48 ng/L). In a recent review by Bu et al. sulfa- (Padhye et al., 2014). The level of ciprofloxacin in this study was lower
methazine, sulfamethoxazole, and sulfadiazine were most frequently than that in Guangzhou and American (Wang et al., 2009; Mu et al.,
detected in surface waters of China (Bu et al., 2013). It showed that 2017). For anti-inflammatory drug, only 4-acetaminopyrine was de-
these compounds were known to be extensively used as veterinary tected with the maximum concentration of 48.16 ng/L 4-acet-
medication in China. On a whole, quinolone showed low level with aminopyrine is one metabolite of metamizole, which is widely used as
highest concentration of 4.04 ng/L. This result was similar to that re- veterinary drug in China. The residue limit is 200 μg/kg (calculated as
ported by Leung (Leung et al., 2013). Their study found thiamphenicol, 4-methylaminoantipyrine) (Announcement of the Ministry of
sulfamethazine and sulfamethoxazole were widely detected in Yangtze Agriculture, No. 235, 2002), while it was prohibited by some countries
River Delta and Pearl River Delta, while quinolone wasn't detected. For such as American and Sweden (Shen et al., 2010).
instance, thiamphenicol was found to be 104.3, 38.2 and 26.5 ng/L in Similarly, only three cardiovascular drugs were frequently detected
Hangzhou, Nanjing and Shanghai. Sulfamethazine and sulfamethox- as shown in Fig. 1. They were valsartan, irbesartan and hydro-
azole were widely detected in Yangtze River Delta and Pearl River Delta chlorothiazide, which accounted for 36%, 31% and 27% of total car-
with highest concentration of 89.6 ng/L (Shanghai) and 21.2 ng/L diovascular drugs, with highest concentration of 66.84, 38.35 and
(Guangzhou) (Leung et al., 2013). It deserved to mention that the whole 33.13 ng/L respectively. However, they hadn't been detected in Spain
level of antibiotics in this study have been decreased slightly compared and American (Maria et al., 2011; Furlong et al., 2017). It could result
to the concentration from the above data, which showed regulation of from the different capacity of water treatment since irbesartan and
antibiotic have played a role in recently years. The level of cipro- valsartan were detected in raw water with high concentration of 830
floxacin was lower than those in Guangzhou with concentration of and 1300 ng/L, while those weren't detected in finishing water (Maria
212 ng/L (Wang et al., 2009). et al., 2011). Remarkably, β-blocks were generally below 0.1 ng/L, and
The concentration of phenicols in tap water in this study was far only accounted for 1% of all cardiovascular drugs. For example, ate-
higher than those in Spain, where thiamphenicol and chloramphenicol nolol was detected with the maximum concentration of 0.07 ng/L. In
were only 7 and 2 ng/L with detection frequency of 75% and 12.5% contrast, it was detected with a frequency of 47% and measured max-
(Carmona et al., 2014). The phenomenon was also appropriate for imum concentration of 53 ng/L in Canada (Khan and Nicell, 2015). The
sulfamethazine and sulfadiazine as shown in Table 1. However, sulfa- phenomenon indicated that the residue of cardiovascular drugs in
methoxazole, ciprofloxacin and trimethoprim were also frequently de- Shanghai was different from other developed countries. There were
tected in worldwide. In this study, the level of sulfamethoxazole was high chatain drugs and low β-blocks in tap water in Shanghai, which
comparable to domestic level (Lin et al., 2016; Qiao et al., 2011; Yang was opposite to other countries.

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M. Liu, et al. Ecotoxicology and Environmental Safety 183 (2019) 109497

For typical psychotropic drug, the concentration of primidone, with F2, and those ranged from 332 to 361 ng/L for D1, D2, D3 and D4. It
maximum concentration of 32.85 ng/L, was higher than that in Spain meant there were similar capabilities of water treatment among water
(ND)(Maria et al., 2011). While the level of carbamazepine, with treatment plants under the management of the same companies.
maximum concentration of 9.70 ng/L, was slightly higher than previous Antibiotics were the dominated compounds in tap water that ac-
work by Wu (2.5 ng/L) (Wu et al., 2015), and far lower than in- counted for over 50% of the total of PPCPs, whether the total of PPCPs
American (25, 140 and 588 ng/L) and Canadian (601 ng/L) (Padhye was high or low in a tap water. The maximum residue happened in D
et al., 2014; Stackelberg et al., 2007; Furlong et al., 2017; Kleywegt and J districts with average of 196 and 183 ng/L, followed by Cb with
et al., 2011). The results showed mental stress was increasing in average value of 142 ng/L. The lowest average value of antibiotic could
Shanghai, but still lower than that in developed countries. reach 63.5 ng/L in central districts (A, B and Ca). The concentrations of
Similarly, BPA had the maximum value of 31.5 ng/L with detection other types of PPCPs in tap water of central districts were less than
frequency of 100%, which showed its widespread existence in tap water 10 ng/L with a few exceptions. It was noticeable that anti-inflammatory
in Shanghai. The concentration of BPA was higher than that in Spain analgesics 4-acetylamino- antipyrine (AAA) was only detected in a few
(6 ng/L) (Carmona et al., 2014), but far lower than in American waters such as D and J. AAA could be removed and it was only detected
(220 ng/L) and Canadian (99 ng/L) (Stackelberg et al., 2007; Kleywegt at low concentrations in a few samples of purified drinking water
et al., 2011). It was also found that artificial sweetener and pre- (Zuehlke et al., 2007). It was probably due to the weak capacity of
servative, as emerging contaminants, were detected in most samples. water treatment for D and J resulted in high residue.
With the growth of live standard, these two types of products were Cardiovascular drugs were commonly occurred in tap water of
widely used in the world. The annual global production capacity of suburb and it's the second highest concentration for the total of PPCPs,
artificial sweeteners reached 15,000 t (Pal et al., 2014). especially for I1 and I2 with the concentrations of 90.8 and 80.1 ng/L,
followed by D1 and D2 with the concentrations of 51.8 and 53.2 ng/L.
3.2. The characteristic of PPCPs in water supply system The presence of cardiovascular in tap water supplies largely resulted
from the aquatic releases of wastewaters from domestic sewage in-
The profile of PPCPs in tap water supplied by different water cluding sewage treatment plants and direct discharge (Cunningham
et al., 2009).
treatment plants was showed in Fig. 2. Different letters represented
different water supplied companies, which are unanimous to adminis- For psychotropic drugs and enzyme inhibitor, there were generally
occurred in tap water with concentrations less than 20 ng/L except for a
trative districts except central districts supplied by water supplied
company B and Ca. The same letter with different numbers represented few exceptions. Their concentrations in tap water of suburb were
slightly higher than those in central districts. The maximum con-
different water treatment plants managed by the same water supplied
companies. centration of psychotropic drugs happened in H1 and H2 with values of
37.6 and 38.1 ng/L, followed by D2 with value of 30.2 ng/L. While the
maximum concentration of dicyclohexylamine happened in H3 with
3.2.1. The characteristic of PPCPs in water treatment plants value of 42.3 ng/L, followed by H2 with value of 21.4 ng/L.
A shown in Fig. 2, it could be seen that the detection frequency of Dicyclohexylamine are formed as byproducts during the synthesis of
PPCPs were closed between 50% and 70% in most water treatment substituted hydrazines, which are well known as pesticides, drugs and
plants with the concentration ranging from 71.6 to 361 ng/L. The synthetic building blocks for heterocyclic synthesis. Up to now, there is
concentration of a few samples, such as D1, D2, D3, D4 and J2, ex- no reported about it in the environment in China. However, its con-
ceeded 300 ng/L, with the highest concentration of 361 ng/L in D4. It centration was so high up to 2 mg/L in the surface water near to in-
was followed by Cb1, Cb2, H1, H2 and H3 with concentration of dustrial origin in Indian (Dsikowitzky et al., 2014). It should be no-
200–300 ng/L. The total concentrations of PPCPs were less than ticeable to the level in surface water in China as a chemical industry
100 ng/L in only five samples. Those were A2, A3, A5, B2, Ca1 and I3. production and use of large countries.
In addition, it could be found that the levels of PPCPs were closed The residues of various types of PPCPs were different in tap water,
when tap waters were supplied by the same companies, while different which indicated that the treatment capacity may quite different among
companies supplied tap water with different level of PPCPs. For ex- water treatment plants. Most types of PPCPs had high residues in D
ample, the concentrations of PPCPs were 108 and 115 ng/L for F1 and

Fig. 2. Detection frequency and concentration of PPCPs in tap water.

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M. Liu, et al. Ecotoxicology and Environmental Safety 183 (2019) 109497

district. Antibiotic and cardiovascular drug were ubiquitous high con- H, J and Cb. All of districts with high level of PPCPs were located in the
centration in J, H, I and Cb districts. While psychotropic drugs and suburbs. On the contrary, there were low levels of PPCPs in the central
dicyclohexylamine also showed high level residues in H district. districts (A, Ca and B). The results showed the capabilities of water
treatment of companies located in central districts were superior to
3.2.2. Effect of source water those in suburbs on the whole.
There are four water sources in Shanghai. For the same water
sources, the level of PPCPs showed different characteristic in the tap 3.3. Health risk assessment
water. For example, raw water in A, B and Ca districts supplied by the
same sources S1, the total concentrations of PPCPs in most tap waters Risk evaluation could only be performed for 34 PPCPs since the
were less than 100 ng/L, which indicated comparable capability of other PPCPs weren't detected, and some ADI values couldn't be found.
water treatment among 12 water treatment plants. The low level of After statistic, it was found that only 9 PPCPs with maximum RQ over
PPCPs could be contributed to advanced capability of water treatment, 10-3. Fig. 5 gives their RQs for different life stages. All results of the
and also good quality of source S1, which is a new water source located human risk assessment were shown in Table S4. For all PPCPs, the age
in stem of Yangzte River. While different levels of PPCPs were detected interval that corresponded to a higher risk quotient was the 9 months-2
in tap water of E, F, G, H and I district ranging from 127 to 251 ng/L, year due to lower body weight and relatively high water consumption.
whose source waters was supplied by the same water source S3. The This result was different from reported results that the high risk was 0–3
total of PPCPs in E, F and G were lower than those in H and I districts. month infant for the different reference values of the 50% of body
The difference was mainly embodied on the content of cardiovascular weight and drinking water intakes between UESPA and China (Gaffney
and psychotropic drugs. The source water of Cb and D districts, source et al., 2015; Lin et al., 2016). In this study, exposure factors of Chinese
water supplied by the same water source S2, While the levels of PPCPs population were adopted. For example, for 0–3month infant, body
in tap water supplied by D company was obviously higher than those weight is 6.4 kg and DWI is only 0.182 L in Chinese, while the two
supplied by Ca, which also reflected the ability to remove cardiovas- reference values are 5.6 kg and 1.15 L. Low water consumption resulted
cular and psychotropic drugs and anti-inflammatory analgesics, espe- in low risk in China.
cially for anti-inflammatory analgesics AAA. It could be removed Overall, no PPCPs presented a RQ ≥ 1. These low values imply that
completely at Ca, while it reached 42.77 ng/L AAA in D3. It hinted that all PPCPs pose a negligible risk to human health when considered in-
the capability of water treatment of D was worse than that of Ca. dividually. However, RQs in infants (9 months–2 years) were 2–3 times
However, for C, it received source water from S1 and S2 to central greater than RQs throughout adolescence and adult. PPCPs with higher
district Ca and suburb Cb, respectively. It could be seen that the total RQ were primidone (RQ = 0.145), valsartan (RQ = 0.093) and irbe-
concentration of PPCPs in tap water in Ca was lower than those in Cb. It sartan (RQ = 0.071) for infants (9–12 month). Only for infant (6
could be deduced that the remove efficiency of PPCPs were limited months~3years), primidone showed RQ ranging 0.105 to 0.145, all the
when the raw water contained much PPCPs. S2 is located in the riv- other pharmaceuticals presented RQ < 0.1. It's surprised that it wasn't
erside of Yangtze River, which receives a certain amount of municipal phenicols antibiotics but cardiovascular and psychotropic drug with
waste water. The reason of high level of PPCPs in tap water of J may high risk. For example, RQs of thiamphenicol and florfenicol were
also be that its water source is closed to Chongming island, where a lower than those of primidone and valsartan, although the formers had
large number of livestock farms located. Much antibiotics and anti-in- far more concentration than those of latters. The reason was that phe-
flammatory analgesics have been used for veterinary medicine pur- nicols had low ADI values. It's uncertain that some adverse effects, such
poses. as resistance and resistance genes, weren't considered when ADI values
of antibiotics were deduced. It warned us that it should pay more at-
3.2.3. Clustering analysis tention to regulate PPCPs with more toxicity of cardiovascular and
All type of PPCPs exhibited significant difference (P < 0.05) among psychotropic drug and theirs sources, such as domestic sewage treat-
35 tap water. Most type was classified to three groups as shown in ment plant.
Table 2. Most tap waters were clustering a group 3. While H, I, J, D and
Cb were classified to group1 or group2 since those included high level 4. Conclusion
PPCPs. According to the total of PPCPs, all of samples were clustered to
3 categories as shown in Fig. 3. Most tap waters were classified to one PPCPs were investigated in tap water from 35 water treatment
group including 18 tap waters such as A1, B1, F1, F2 and so on. In the plants covering all districts and water supply companies in Shanghai.
group, the level of PPCPs was the lowest among the three groups. The PPCPs commonly existed in tap water mainly including phenicols an-
second group included 11 tap waters such as Cb1, H1, and so on. The tibiotics, chatain cardiovascular drugs, psychotropic drug and AAA. On
highest residues happened in the last group only including 6 tap waters, the whole, the level of PPCPs in central districts was lower than those in
those were D1, D2, D3, D4, J2 and J3. It could be found that most suburb. The residues of PPCPs were similar in the same district, while
samples came from same water supplied company were classified to the different characteristic were exhibited among some districts. High re-
same group, which also showed the level PPCPs of tap water more af- sidues of PPCPs in tap water happened in Cab, D, H, I and J districts.
fected by water treatment capacity than raw water. The detected PPCPs in tap water should not pose adverse risks to human
Map of PPCPs was plotted as show in Fig. 4. It could be clearly seen health. However, few cardiovascular and psychotropic drugs posed
that the highest concentration of PPCPs was located at D, followed by potential risk to infants, especially for those lived in D and H districts. It

Table 2
Cluster analysis (P ≥ 0.05) of PPCPs in tap water.
Type of PPCPs group 1 group 2 group 3

Antibiotic Ca Cb1,Cb2,Cb4,D1, D2,D3,D4,J1,J2,J3 Others

Cardiovascular drug Cb1,Cb2,Cb4,D1,D2,D3,D4,E1,E2,G1,H1,H2,H3, J2,J3 I1,I2 Others
Psychotropic drugs Cb1，D2,D3,H3 H1,H2 Others
Anti-demal allergyic agent H2 H3 Others
Enzyme inhibitor H2 H3 Others
Anti-inflammatory analgesics D1,D2,D3,D4,J2 H1，J3 Others

6
M. Liu, et al. Ecotoxicology and Environmental Safety 183 (2019) 109497

Fig. 3. Dendrogram of all the samples by cluster analysis of the total concentration of PPCPs.

Fig. 4. Map of PPCPs in tap water covering all districts of Shanghai.

7
M. Liu, et al. Ecotoxicology and Environmental Safety 183 (2019) 109497

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