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. Author manuscript; available in PMC: 2023 Dec 11.
Published in final edited form as: Sci Total Environ. 2022 Aug 17;851(Pt 1):158102. doi: 10.1016/j.scitotenv.2022.158102

Occurrence of primary aromatic amines and nicotine in sediments collected from the United States

Magdalena Urbaniak 1,2,a, Sridhar Chinthakindi 2,a, Andres Martinez 3, Keri C Hornbuckle 3, Kurunthachalam Kannan 2,*
PMCID: PMC10116586  NIHMSID: NIHMS1891567  PMID: 35987249

Abstract

Despite extensive use of primary aromatic amines (AAs) in consumer products, little is known about their occurrence in the environment. In this study, we investigated the occurrence of 14 AAs and nicotine in 75 sediment samples collected from seven estuarine and freshwater ecosystems in the Unites States. Additionally, risk quotients (RQs) were calculated to assess potential risks of these chemicals to aquatic organisms. Of the 14 AAs analyzed, seven of them were found in sediments. The sum concentrations of seven AAs in sediments were in the range of 10.2 to 1810 ng/g, dry wt (mean: 388 ng/g). Aniline was the most abundant compound, accounting for, on average, 53% of the total concentrations. Nicotine was found in sediments at a concentration range of <LOQ to 1340 ng/g, dry wt (mean: 119 ng/g). Among the seven sampling locations studied, AAs and nicotine concentrations were the highest in sediment from Altavista wastewater lagoon in Virginia (AV, mean: 1700 ng/g) followed in descending order by Chicago Sanitary and Ship Canal (CSSC, mean: 807 ng/g), Indiana Harbor and Ship Canal (IHSC, mean: 698 ng/g) and New Bedford Harbor (NBH, mean: 482 ng/g). Sediments from the upper Mississippi River (MISS, mean: 63.4 ng/g) and Tittabawassee River (TBR, mean: 52.3 ng/g) contained the lowest concentrations. The RQ values for AAs in sediment ranged from 0 to 733 and that for nicotine ranged from 0 to 2060. Among AAs, the highest RQ value was found for 4-chloroaniline. Nicotine exhibited notable RQ values, which suggested risk from this chemical to aquatic organisms. This is the first study to report the occurrence of AAs in sediments and our results suggest the need for further investigations on the sources and ecological impacts of these chemicals in aquatic ecosystems.

Keywords: aromatic amine, aniline, sediment, risk, nicotine

Graphical abstract

graphic file with name nihms-1891567-f0001.jpg

1. Introduction

Primary aromatic amines (AAs) are organic chemicals consisting of an aromatic ring attached to an amine, and are building blocks in the production of textile dyes, agrochemicals, and other synthetic chemicals (IARC, 2010a). For decades, AAs were produced in large quantities for the manufacture of food colorants, textiles, rubber, pharmaceuticals, cosmetics, pesticides, and explosives (Favaro Perez et al., 2021; Padahe et al., 2021; Merkel et al., 2018; Campanella et al., 2015; Ros et al., 2012; Johnson et al., 2010; Andrew et al., 2004; Turesky et al., 2003). Aniline, the building block of AAs, is a high production volume chemical (USEPA, 2020; OECD, 2009; Käfferlein et al., 2014), with a global production of 8.4 million tons in 2020 (Mohammed et al., 2020). The production of aniline in the USA in 2011 was ~887 000 tons, whereas that in 2012–2015, it was 2.3 million tons (ChemView, 2016). The USA is also the third-largest consumer of aniline, accounting for 17% of its global consumption (IHS Markit, 2019). AAs are also found in cigarette butts, tobacco smoke and diesel exhaust (Dobaradaran et al., 2022; WHO, 2021). Nicotine is a constituent of tobacco smoke, with annual global consumption of ~50 000 tons (WHO, 2021; van Wel et al., 2016).

Studies have shown that AAs and nicotine are carcinogenic and endocrine disrupting chemicals, which can enter the aquatic environment through the discharge of wastewater (Weber et al., 2001; Government Canada, 1994). Based on a model, the UNEP (2005) reported that the major sink for AAs in the environment is aquatic ecosystems (84%) followed by atmosphere (16%). Studies have reported the occurrence of AAs in surface-, ground- and drinking water at concentrations ranging from 500 ng/L in drinking water to 20,000 mg/L in wastewater (Neurath et al., 1977; Greve and Wegman, 1975; Meijers and van der Leer, 1976; Herzel and Schmidt, 1977; Shackelford and Keith, 1976; Hushon et al., 1980; Government Canada, 1994; Rockett et al., 2014; Anastacio Ferraz et al., 2012; He et al., 2014; Albahnasawi et al., 2020). Aquatic environment is the major sink for nicotine (93%), followed by soil (4%) and air (3%) (Seckar et al., 2008). High concentrations of nicotine have been found in wastewater (up to 424,000 ng/L) and surface water ( up to 9,340 ng/L) (Verovsek et al., 2022; Oropesa et al., 2017; Benotti and Brownawell, 2007; Wang et al., 2001; Kaiser et al., 1996). Studies have also shown that 80% of AAs, especially aniline, are covalently bound in sediments with half-lives of approximately 3500 days (Weber et al., 2001; ECHA, 2019; Giersing et al., 2009). Thus, sediments can be a sink for AAs in the aquatic environment. Although recent studies reported occurrence of AAs and nicotine in human urine and indoor dust (Chinthakindi et al., 2022; Chinthakindi and Kannan, 2022a,b; Chinthakindi and Kannan, 2021), there is limited information on the magnitude of contamination by these compounds in the aquatic ecosystems (ChemView, 2016; IHS Markit, 2019).

To our knowledge, this is the first study to report the occurence of AAs and nicotine simultaneously in sediments from US aquatic ecosystems. The aim of this study was to determine the concentrations and frequency of occurrence of 14 AAs and nicotine in 75 sediment samples collected from seven freshwater and estuarine ecosystems in the United States. We further assessed ecological risks of AAs and nicotine in sediments, based on the reported, predicted no-effect concentrations (PNEC) in sediment for these chemicals.

2. Materials and methods

2.1. Sampling

A total of 75 sediment samples were collected between 2004 and 2017 from seven water bodies covering six states in the United States: New Bedford Harbor (NBH, n=24; collected in 2017), Massachusetts; Chicago Sanitary and Ship Canal (CSSC, n=9, collected in 2013), Illinois; Altavista wastewater lagoon (AV, n=6, collected in 2015), Virginia; Upper Mississippi River (MISS, n=13, collected in 2012), Iowa; Indiana Harbor and Ship Canal (IHSC, n=3, collected in 2006), Indiana; and Saginaw Bay (SB, n=8, collected in 2004) and Tittabawassee River (TBR, n=11, collected in 2004), Michigan. Further details of the samples are provided in the Supplementary Information (Table S1. Fig. S1). Sediment samples were collected using a dredge or grab sampler. Surface sediment (0–12”) was used for analysis. Sediment sample from each location was homogenized, and stored in pre-cleaned amber jars, and transported to the laboratory. Prior analysis samples were freeze-dried and stored at −20 °C.

2.2. Chemicals and reagents

Fifteen native standards (NS) and 9 isotopically labeled internal standards (IS)(see Table S2 for chemical names and their abbreviations) of 95–99% purity were purchased from Toronto Research Chemicals (TRC; Toronto, ON, Canada), AccuStandard (New Haven, CT, USA) and Sigma-Aldrich (St. Louis, MO, USA). The names of target analytes, abbreviations and Chemical Abstracts Service (CAS) numbers are shown in Table S2. High-performance liquid chromatography (HPLC)-grade solvents, namely water, methanol, and methyl t-butyl ether (MTBE) were purchased from J. T. Baker (Center Valley, PA, USA). Analytical-grade formic acid (HCOOH), sodium hydroxide (NaOH), and hydrochloric acid (HCl; 37%, v/v) were purchased from Sigma-Aldrich. Glass tubes (16 × 100 mm) were purchased from Fisher Scientific (Waltham, MA, USA).

2.3. Chemical analysis

Sediment samples were extracted by ultrasonication. Briefly, 0.5 g of freeze-dried sediment was weighed into a glass tube, fortified with 10 ng each of isotopically labeled IS, and equilibrated for 30 min. Four milliliters of HPLC grade water and 50 µL of 10 M NaOH were added, vortexed for 1 min, and sonicated (at 40 kHz) at room temperature (22°C) using a Branson 3510 R-DTH sonicator for 30 min (Branson Ultrasonics Corporation, Danbury, CT, USA) followed by shaking on an orbital shaker (at 180 strokes per min) for 30 min (Eberbach Corp., Ann Arbor, MI, USA). Samples were centrifuged at 2880 × g for 20 min (Eppendorf Centrifuge 5804, Hamburg, Germany) and the aqueous layer was transferred into a 15 mL polypropylene (PP) tube. The aqueous layer was extracted with 3 mL of MTBE by shaking in an orbital shaker at 180 strokes per min for 30 min and then centrifuged at 2880 × g for 10 min. The MTBE layer was transferred into another 15 mL PP tube and the extraction was repeated with additional 3 mL of MTBE. The MTBE extracts were combined and fortified with 15 µL of 0.25M HCl and evaporated to near-dryness under a gentle N2 stream. The residue was then reconstituted with 200 µL of water: methanol mixture (9:1 v/v) and transferred into a vial with a 300 µL glass insert for instrumental analysis.

2.4. Instrumental analysis

Analysis of AAs and nicotine was performed on a Shimadzu LC-30 AD series HPLC coupled to a Sciex QTRAP 5500 tandem mass spectrometer (MS/MS; Applied Biosystems, Foster City, CA, USA). Target analytes were chromatographically separated on an Ultra BiPh column (100 mm × 2.1 mm, 5 µm; Restek, Bellefonte, PA, USA) connected to a Betasil C18 guard column (20 mm × 2.1 mm, 5 µm; Thermo Scientific, West Palm Beach, FL, USA) using formic acid (0.1%) in a water/methanol mixture (95:5, v/v) (A), and 0.1% formic acid in methanol (B) as the mobile phases. The mobile phase gradient program was as follows: 95% A (min 0), 95%–58% A (min 0.01–2.50), 58%–25% A (min 2.50–6.50), 25%–5% A and a hold for 1 min (min 6.50–8.70), 5%–95% A (min 8.70–9.70), and a hold for 2.50 min (min 9.70–10.00), for a total run time of 12.5 min. The mobile phase flow rate was 0.3 mL/min and the sample injection volume was 5 µL.

Identification of target analytes was performed using multiple reaction monitoring (MRM) in electrospray positive ionization mode (ESI+-MS/MS). The compound-specific MS/MS parameters including collision energy, declustering potential, entrance potential, and collision exit potential were optimized, and are summarized in Table S2. The MS ion source temperature and ion spray voltage were set at 500°C and 4500 V, respectively. The collision gas and curtain gas flow rates were set at 8 and 20 psi, respectively. The gas 1 and gas 2 flow rates were set at 30 and 30 psi, respectively.

2.5. Quality assurance and quality control

The analytes were quantified against an external calibration curve constructed with native and isotopically labeled ISs. Nine of the 15 target analytes had corresponding isotopically labeled IS. For the remaining analytes, IS was selected based on the structural similarity. A nine-point calibration curve, prepared at concentrations of analytes ranging from 0.1 to 50 ng/mL (with 10 ng/mL IS mixture), showed regression coefficients >0.999. Relative recoveries (%) of target analytes were determined in triplicate experiments by fortifying a sediment (sample # 16) at a concentration of 10 ng/g each for both native and internal standards, and passed through the entire analytical procedure. The mean recoveries of target analytes were in the range of 47% (2-aminobiphenyl [ABP]) - 144% (2,6-dimethylaniline [DMA]). The lowest acceptable calibration concentrations divided by a nominal sample weight of 0.5 g were used in the calculation of limits of quantification (LOQs), which were in the range of 0.2–1.0 ng/g, dry wt (Table S3). A solvent blank and a midpoint calibration standard were injected after every 10 samples to monitor for carryover of target analytes and drift in instrumental sensitivity, respectively.

2.6. Risk assessment

A risk quotient (RQ) approach was used in the assessment of potential ecological risks of AAs and nicotine in sediments. RQ values were calculated by dividing the measured AA or nicotine concentration (MEC) in sediment by the predicted no-effect concentration (PNECsed), derived from toxicity studies using aquatic invertebrates namely Daphnia magna, Chironomus riparius or Lumbriculus variegatus (Kucharski et al., 2022):

RQ = MECsed/ PNECsed

where:

MECsed- measured concentration in sediment [ng/g, dry wt].

PNECsed- predicted no-effect concentration in sediment [ng/g, dry wt].

The PNECsed values for aniline, o-anisidine, o/m-toluidine and nicotine have been reported in the literature (Table S10). The PNECsed for p-toluidine was calculated from the reported PNECwater as below:

PNECsed =(Kd/Rhosusp) x PNECwater x1000 (Kucharski et al., 2022)

where:

PNECwater – predicted no-effect concentration in water was 0.12 μg/L (UNEP, 2005).

Kd – distribution coefficient of the chemical between water and sediment.

Rhosusp – bulk density of wet sediment, and we used a value of 1150 kg/m3.

PNECsed for 4-chloroanaliline (4-CA) and 3-chloroaniline (3-CA) were estimated from the results of chronic toxicity studies, by dividing EC50 by a factor of 1000 (Kucharski et al., 2022; ECHA, 2003).

The PNECsed values for aniline, o-anisidine, o-/m-toluidine (o-/m-TD), p-toluidine (p-TD), 4-chloroaniline (4-CA), 3-chloroaniline (3-CA) and nicotine are 153, 8, 2, 2.09, 0.54, 0.54 and 0.65 ng/g, dry wt, respectively. A RQ value of >1 is suggestive of a potential risk posed by the contaminant on sediment dwelling aquatic organisms.

2.7. Data analysis

The non-parametric Kruskal-Wallis test was used to verify whether there are statistically significant differences between the concentrations among different sites. Another non-parametric test, Mann-Whitney pairwise test, was used to compare differences in concentrations between samples collected from two different locations. The significance was set at p≤0.05. The correlation between AAs and nicotine was tested using Spearman’s correlation test. Principal component analysis (PCA) was performed to evaluate the multivariate ordination of AAs and nicotine concentrations among various locations. Prior to performing the PCA, the raw data were normalized by subtracting from the mean value and dividing by the standard deviation. Hierarchical cluster analysis was then performed to determine the differences in concentration patterns among samples. All analyses were performed using PAST 4.0 software. Data are presented on a dry weight basis unless specified otherwise.

3. Results and discussion

3.1. Concentrations of AAs and nicotine in sediments

Of the 14 AAs targeted, seven, namely aniline, o-anisidine, o-/m-TD, p-TD, 3-CA, 4-CA and 4-chloro-o-toluidine (4-CTD), were found in sediments and their sum concentrations (∑7AAs) ranged from 10.2 (TBR) to 1810 ng/g, dry wt (AV) (Table 1). The concentrations were significantly different among the seven water bodies studied (Kruskal-Wallis test, p≤0.05; Table S4). The lowest mean concentrations of ∑7AAs were found in sediments from the TBR (51.8 ng/g) and the MISS (60.1 ng/g) whereas the highest mean concentrations were measured in sediments from AV (935 ng/g), followed by CSSC (697 ng/g), IHSC (615 ng/g), NBH (482 ng/g), and SB (275 ng/g). For nicotine, the highest mean concentrations were found in sediments from AV (760 ng/g), followed in decreasing order by CSSC (129 ng/g), NBH (112 ng/g), IHSC (83.4 ng/g) MISS (3.27 ng/g) and TBR (0.480 ng/g) (Table 1). Nicotine concentrations in sediment from AV were significantly higher than those in other samples (Mann-Whitney pairwise test, p≤0.05; Table S7).

Table 1.

Concentrations (ng/g, dry weight) of primary aromatic amines and nicotine in sediments collected from seven waterbodies in the United States.1

Sampling Location aniline o-anisidine o/m-TD p-TD 4-CA 3-CA 4-CTD ∑AAs nicotine
NBH -New Bedford Harbor, Massachusetts (n = 24) min 119 3.86 5.58 19.8 32.7 <LOQ <LOQ 210 23.6
max 730 42.0 87.4 179 175 17.8 11.6 1140 284
mean 307 14.9 27.1 59.1 63.3 6.37 3.35 482 112
median 288 12.6 22.8 41.9 52.4 5.22 2.63 434 97.2
DF (%) 100 100 100 100 100 80.9 95.8 100
CSSC -Chicago Sanitary and Ship Canal, Illinois (n = 9) min 29.1 1.52 3.90 7.19 11.8 2.59 <LOQ 56.2 9.73
max 557 325 143 155 181 110 26.5 1130 314
mean 321 82.4 57.7 67.4 105 40.2 5.22 679 129
median 353 46.2 54.8 63.4 96.2 35.8 2.77 688 98.9
DF (%) 100 100 100 100 100 100 100 100
AV – Altavista wastewater lagoon, Virginia (n = 6) min 34.5 2.30 4.33 5.01 24.4 22.1 2.03 116 262
max 509 407 55.1 93.7 395 330 76.0 1800 1340
mean 303 182 28.2 41.8 204 154 22.0 935 760
median 300 158 26.9 36.6 179 159 14.2 867 757
DF (%) 100 100 100 100 100 100 100 100
MISS -Mississippi River, Iowa (n = 13) min 4.73 <LOQ <LOQ <LOQ <LOQ <LOQ nd 13.5 <LOQ
max 66.4 53.7 12.3 29.5 16.3 0.110 nd 135 10.9
mean 31.1 15.2 3.32 5.42 5.04 0.0200 nd 60.1 3.27
median 26.1 8.04 2.35 2.41 4.02 0.00 nd 60.5 1.73
DF (%) 100 84.7 92.3 69.3 76.9 15.3 nd 76.9
IHSC - Indiana Harbor and Ship Canal, Indiana (n = 3) min 108 1.27 43.2 90.3 27.9 <LOQ nd 271 42.6
max 433 3.73 97.3 306 102 4.12 nd 942 117
mean 280 2.77 69.2 204 57.7 1.37 nd 615 83.7
median 299 3.31 67.0 214 43.8 0.00 nd 632 91.4
DF (%) 100 100 100 100 100 33.3 nd 100
SB - Saginaw Bay, Lake Huron, Michigan (n = 8) min 15.5 4.25 4.03 4.78 <LOQ <LOQ nd 32.6 0.00
max 569 27.2 25.6 64.5 45.9 9.73 nd 709 23.5
mean 198 10.4 16.0 25.4 21.9 3.28 nd 275 10.5
median 144 6.42 17.3 17.5 23.2 2.02 nd 241 8.02
DF (%) 100 100 100 100 100 50.0 nd 75.0
TBR - Tittabawassee River, Michigan (n = 11) min 4.22 3.05 <LOQ <LOQ 0.08 0.00 nd 10.2 0.00
max 169 25.5 34.7 16.4 20.1 0.00 nd 266 4.69
mean 30.9 7.84 6.16 2.42 4.48 0.00 nd 51.8 0.48
median 16.7 5.42 2.58 0.00 2.92 0.00 nd 32.1 0.00
DF (%) 100 100 72.7 45.4 100 0.00 nd 36.3
min 4.22 <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ 10.25 <LOQ
Total (n=75) max 730 408 143 307 396 331 76.0 1800 1340
mean 206 34.7 24.1 43.1 56.1 19.9 3.51 388 119
median 169 11.6 15.9 28.0 36.6 0.550 0.470 303 35.9
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1

Aniline; o-anisidine; o/m-TD, ortho/meta-toluidine; p-TD, para-toluidine; 4-CA, 4-chloroaniline; 3-CA, 3-chloroaniline; 4-CTD, 4-chloro-o-toluidine; nicotine. nd - not detected. DF- detection frequency; LOQ- limit of quantification.

Among seven AAs, aniline was the most abundant compound found in all sediment samples (Table 1). The highest and lowest aniline concentrations were found in sediments from NBH (range: 119–730 ng/g, mean: 307 ng/g) and the TBR (4.22–169 ng/g, 30.9 ng/g), respectively. 4-CA was the second abundant AA found in all sediment samples. The highest concentrations of 4-CA were found in sediment collected from AV (24.4–395 ng/g, 204 ng/g) and the lowest concentrations were found in sediments from the TBR (0.0800–20.1 ng/g, 4.48 ng/g).

The percentage composition of individual AA to the sum of the mean concentration of seven AAs (∑7AAs) is shown in Fig. 1. Aniline accounted for 32.4% to 72.0% of the ∑7AAs concentrations, with a mean value of 53.0% (Fig.1), followed in descending order by 4-CA (range: 8.00%−21.8%, mean: 12.0%), p-TD (4.50%−33.1%, 11.9%), and o-anisidine (0.500%−25.2%, 11.3%). The proportion of o/m-TD and 3-CA in ∑7AAs concentrations was <8.00% and <4.00%, respectively (Fig. 1). Besides being used in several products including dyes, rubber, herbicides and pharmaceuticals (USEPA, 2020; OECD, 2009; Käfferlein et al., 2014), aniline, the simplest of AA, is formed from the degradation of several other AAs (Arora, 2015; Chinthakindi et al., 2022). This would explain elevated composition of aniline in sediments. 4-CA is a high production volume chemical with an annual production of 250–500 tons in 2016 in the United States and is used in the manufacture of dyes, pesticides and drugs. o-Anisidine was reported to be present at high concentrations in freshly smoked and aged cigarette butts (Dobaradaran et al., 2022).

Fig 1.

Fig 1.

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Composition profiles (%) of primary aromatic amines in sediments collected from the United States (NBH – New Bedford Harbor; CSSC – Chicago Sanitary and Ship Canal; AV- Altavista wastewater lagoon; MISS – upper Mississippi River; IHSC – Indiana Harbor and Ship Canal; SB -Saginaw Bay; TBR – Tittabawassee River; o/m-TD - ortho/meta-toluidine; p-TD- para-toluidine; 4-CA- 4-chloroaniline; 3-CA- 3-chloroaniline; 4-CTD- 4-chloro-o-toluidine).

Our results suggest the widespread occurrence of AAs and nicotine in sediment from freshwater and estuarine waters in the United States. Aniline and several other AAs have been used in more than 300 consumer products (Chinthakindi and Kannan, 2021). These chemicals may arise from dyes, rubber, varnishes, cosmetics, polyurethane foam, and agrochemicals (Albahnasawi et al., 2020; He et al., 2014; Rockett et al., 2014; Anastacio Ferraz et al., 2012; Weber et al., 2001; Rippen, 1990). Earlier studies have reported elevated concentrations of AAs and nicotine in untreated wastewater (up to 5780 ng/L) and textile sludge (up to 82500 ng/g) (Gracia-Lor et al., 2020; Zheng et al., 2020; Van Wel et al., 2016; Ning et al., 2015; Senta et al., 2015). The high concentrations of AAs and nicotine found in AV can be, therefore, related to sources arising from industrial sewage (SAP, 2005). In fact, sediments from AV were collected from a wastewater lagoon, which received discharges from local textile and furniture industries (e.g. Burlington Industries, Lane Furniture Company) (SAP, 2005; VADEQ, 1999), and that would explain the highest concentrations of AAs and nicotine found in those samples. Studies reporting AA concentrations in sediments are scarce. Akyuz and Ata (2006) reported aniline, m-toluidine, 3-CA and 4-CA in sediments from Turkey at mean concentrations 192, 0.35, 10.4 and 0.19 ng/kg, dry wt, respectively. Jurado-Sanchez et al. (2013), found five AA compounds namely aniline, 2-CA, 3-CA, 2,4,5-trichloroaniline and 2,4,6-trichloroaniline in sediments from Spain at concentrations ranging from 0.40 to 1.3 ng/g, dry wt. The reported concentrations of aniline, m-toluidine, 3-CA and 4-CA from Turkey and Spain are much lower than those found in our study. In China, Hu et al. (2020) measured concentrations of five AAs namely, phenylamine, 4-chlorophenylamine, 1-naphthalenamine, diphenylamine, and 4-aminobiphenyl in sediments from Dianchi Lake, at a mean total concentration of 19 ng/g, dry wt. Feng et al. (2007) reported concentrations of two AAs, namely, phenylamine and benzidine in sediments from Zhenjian, Yixing, and Changzhou (China) in the range of <LOD to 55 ng/g, dry wt. However, our study was focused on a different set of AAs and direct comparison with the studies from China was not possible. To our knowledge no other studies are available for comparison of AAs concentrations in sediments.

3.2. PCA and correlation analysis

The principal component analysis (PCA) of AA and nicotine concentrations in sediments distinguished less polluted areas (i.e. TBR and MISS) from more highly polluted ones (i.e. CSSC, IHSC and NBH) (Fig. 2). Sediment from AV lagoon, containing the highest concentrations of AAs and nicotine, clustered separately, while sediments from SB with moderate concentrations of AAs, clustered between low- and high- concentration samples. The PCA also displayed a significant contribution of aniline, o/m-TD and p-TD in sediments collected from NBH and CSSC, confirming that these three compounds accounted for most of ∑7AAs concentrations (see Fig. 1). Aniline, o/m-TD, and p-TD correlated positively in principal component 1 (PC1), which explained 60% of the total variance in AAs concentrations. The loadings for o-anisidine, 3-CA and 4-CTD were correlated in principal component 2 (PC2) (24% of the total variance) and with samples collected from AV lagoon (Fig. 2); the three compounds were dominant in AV lagoon sediment samples accounting for 38% of ∑7AAs concentrations (see Fig.1). The loading for nicotine was also correlated in PC2, concurrence with the high concentration of this compound found in AV lagoon sediment samples. The results of PCA were further confirmed by the hierarchical cluster analysis, which showed that AA patterns in sediments from the TBR and MISS were related (the smallest distance), whereas those of AV were farthest in comparison to other sampling sites (Fig. S2).

Fig. 2.

Fig. 2.

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Scatterplot of scores of principal component analysis of concentrations of aromatic amines and nicotine in sediment samples collected from the United States (NBH – New Bedford Harbor; CSSC – Chicago Sanitary and Ship Canal; AV- Altavista wastewater lagoon; MISS – upper Mississippi River; IHSC – Indiana Harbor and Ship Canal; SB - Saginaw Bay; TBR – Tittabawassee River; o/m-TD - ortho/meta-toluidine; p-TD- para-toluidine; 4-CA- 4-chloroaniline; 3-CA- 3-chloroaniline; 4-CTD- 4-chloro-o-toluidine).

Spearman’s correlation analysis demonstrated strong positive correlations between aniline and o/m-TD (correlation coefficient, rs=0.82), aniline and p-TD (rs=0.86), and aniline and 4-CA (rs=0.87). Similarly, strong correlations were found between 4-CA and 3-CA (rs=0.74) and 4-CA and 4-CTD (rs=0.81) (Fig. 3, Table S9). p-TD is widely used in the production of dyes, pesticides, pharmaceuticals and as antioxidants in rubber and in the production of polyurethane foam (Hanley et al., 2012; IARC, 2010b; Marand et al., 2004). o/m-TD is an impurity in p-TD formulations. The concentrations of o/m-TD were, on average, 2-fold lower than p-TD concentrations (Table 1). 4-CA is used as an intermediate in the production of colorants for drugs, textiles, cosmetics, tattoo inks, and hair dyes (WHO, 2003). Thus, the significant correlation between aniline and o/m-TD, p-TD, and 4-CA may imply environmental transformation of the latter three compounds into aniline (Kaufman and Blake, 1973). Similar correlations were reported in earlier studies of AAs in indoor dust (Chinthakindi and Kannan, 2022; Chinthakindi et al., 2021). Nicotine was strongly correlated with 4-CA (rs=0.87), p-TD (rs=0.78), aniline (rs=0.77), and o/m-TD (rs=0.68) (Fig. 3, Table S9). Aniline, p-TD, and o/m-TD are the major AAs present in tobacco smoke (Shubert et al., 2011; Stabbert et al., 2003; Luceri et al., 1993). The correlation of nicotine with aniline, o/m-TD, p-TD, and 4-CA suggests similar sources of these chemicals. Considering the high consumption of nicotine each year, cigarette butts and smoke are important sources of AAs in the environment.

Fig. 3.

Fig. 3.

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The Spearman correlation coefficients (rs) between individual aromatic amines and nicotine (rs =0.00–0.19 – very week correlation; 0.20–0.39 -weak correlation; 0.40–0.59- moderate correlation; 0.60–0.79 – strong correlation; 0.80–1.00 – very strong correlation; blank spots indicate no significant correlation at p=0.05); (o/m-TD - ortho/meta-toluidine; p-TD- para-toluidine; 4-CA- 4-chloroaniline; 3-CA- 3-chloroaniline; 4-CTD- 4-chloro-o-toluidine).

3.3. Comparison of AAs with other organic compounds in sediments

Concentrations of several organic contaminants were reported in the same set of sediments analyzed in this study and are compiled in Table S8. Sediments from the MISS showed 3-fold higher concentration of ∑7AAs than the concentration reported for polychlorinated biphenyls (PCBs) (Martinez et al., 2016). The concentrations of ∑7AAs in sediments from the TBR were an order of magnitude higher than those of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) (Hilscherova et al., 2003). The mean concentrations of ∑7AAs in SB sediments were four-fold higher than those of PCBs, and an order of magnitude higher than those of PCDDs and PCDFs (Kannan et al., 2008). In contrast, sediments from CSSC contained much lower concentrations of ∑7AAs than those of PCBs, polycyclic aromatic hydrocarbons (PAHs), and organophosphate esters (OPEs) (Peverly et al., 2015). The IHSC is a heavily industrialized urban catchment, and sediments from this canal contained PCBs at concentrations as high as 72000 ng/g (Saktrakulkla et al., 2022; Martinez et al., 2010, 2011), an order of magnitude higher than those of ∑7AAs concentrations. Concentrations of PCBs in sediments from NBH, an urban tidal estuary located in Massachusetts, is on the order of several milligrams per gram (Saktrakulkla et al., 2022), which is two orders of magnitude higher than the concentrations of ∑7AAs measured in our study. PCBs concentrations in AV lagoon sediments (12700 mg/g) (Mattes et al. 2018) were several orders of magnitude higher than those of∑7AAs concentrations. Overall, sediments from MISS, TBR and SB demonstrated higher levels of ∑7AAs in comparison to other legacy organic compounds, whereas samples from heavily contaminated industrial sites such as CSSC, IHSC, NBH and AV contained higher concentrations of legacy organic pollutants (mainly PCBs) than those of ∑7AAs. Further studies on the relationship between AAs and other legacy organic pollutants are needed.

3.4. Ecological risk

The risk quotient (RQ) approach introduced by the US Environmental Protection Agency (USEPA) is a point estimate of exposure and effects (Liu et al., 2018). In this study, RQ values were calculated as the ratios of measured environmental concentration (MEC) in sediment to the predicted no-effect concentration (PNECsed) (Kucharski et al., 2022). The PNECsed values for six AAs and nicotine were derived from chronic toxicity studies of these chemicals on aquatic invertebrates namely Daphnia magna, Chironomus riparius or Lumbriculus variegatus (Table S10).

The RQ values for individual AAs and nicotine are presented in Table 2. The RQs for AAs in several locations exceeded the value of 1.0 (USEPA, 2007). 4-CA exhibited the highest RQs, that ranged from 0 to 733 with mean values for each study site ranging from 8.29 (TBR) to 378 (AV). Aniline showed lower RQs in the range of 0 to 51, with mean values ranging from 0.200 (TBR) to 2.10 (CSSC). One study reported that among four anilines tested (aniline, 4-chloroaniline, 3,5-dichloroaniline and 2,3,4-trichloroaniline), 4-CA was the most toxic and aniline was the least toxic to algae P. subcapitata (Dom et al. 2010). Vazquez and Rial (2014) reported that aniline was less toxic than cyclododecane and naphthalene to selected bacteria (Pseudomonas sp., Phaeobacter sp. and Euconostoc mesenteroides).

Table 2.

Calculated risk quotient (RQ) values for aromatic amines and nicotine in sediments collected from the United States.

Sampling Location   aniline o-anisidine o/m-TD p-TD 4-CA 3-CA nicotine
NBH -New Bedford Harbor, Massachusetts (n = 24) min 0.780 0.480 2.79 9.46 60.7 0 36.3
max 4.77 5.25 43.7 86.0 325 32.9 438
mean 2.01 1.87 13.6 28.3 117 11.8 173
SD 0.980 1.24 8.84 21.9 61 11.3 105
CSSC -Chicago Sanitary and Ship Canal, Illinois (n = 9) min 0.190 0.190 1.95 3.44 21.9 4.81 15.0
max 3.64 40.6 71.4 74.1 335 203 483
mean 2.10 10.3 28.9 32.3 195 74.5 198
SD 0.980 11.7 18.9 21.2 82 54.7 159
AV – Altavista wastewater lagoon, Virginia (n = 6) min 0.23 0.290 2.17 2.39 45 41.1 403
max 3.33 51.0 27.6 44.8 733 613 2060
mean 1.98 22.8 14.1 20.0 378 286 1170
SD 1.20 18.6 8.75 14.4 245 196 483
MISS -Mississippi River, Iowa (n = 13) min 0.03 0 0 0 0 0 0
max 0.43 6.71 6.18 14.1 30.1 0 16.8
mean 0.200 1.89 1.66 2.59 9.34 0 5.03
SD 0.13 2.01 1.66 3.95 8.78 0 5.54
IHSC - Indiana Harbor and Ship Canal, Indiana (n = 3) min 0.710 0.160 21.6 43.2 51.7 0 65.5
max 2.83 0.470 48.7 147 188 7.63 180
mean 1.83 0.350 34.6 97.5 107 2.54 129
SD 0.87 0.130 11.1 42.4 58.6 3.60 47.6
SB - Saginaw Bay, Lake Huron, Michigan (n = 8) min 0.100 0.530 2.02 2.29 0 0 0
max 3.72 3.40 12.8 30.9 85.0 18.0 36.1
mean 1.29 1.31 8.00 12.2 41.0 6.08 16.1
SD 1.22 1.03 4.23 10.5 33.7 6.64 14.3
TBR - Tittabawassee River, Michigan (n = 11) min 0.03 0.380 0 0 0 0 0
max 1.11 3.19 17.4 7.83 37.3 0 7.22
mean 0.200 0.980 3.08 1.16 8.29 0 0.740
SD 0.300 0.760 4.74 2.23 9.66 0 2.06
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1

Aniline; o-anisidine; o/m-TD, ortho/meta-toluidine; p-TD, para-toluidine; 4-CA, 4-chloroaniline; 3-CA, 3-chloroaniline; 4-CTD, 4-chloro-o-toluidine; nicotine

The RQ values for nicotine ranged from 0 (TBR, MISS, SB) to 2060 (AV) with mean values between 0.740 (TBR) and 1170 (AV). The calculated mean and max RQ values for nicotine in AV sediment were notably >1. Ruan and Liu (2015) showed that nicotine at concentrations of 3 to 8 ng/g in sediments significantly reduced microbial diversity. Hiki et al. (2017) demonstrated that among several organic (e.g., PAHs) and inorganic pollutants (e.g., trace metals), nicotine exerted significant toxicity in sediments. Thus, further studies are needed to assess toxicity of nicotine towards aquatic organisms.

4. Conclusions

The study reports the concentrations of seven AAs and nicotine simultaneously in sediments from the United States waterbodies. AAs, especially aniline, o-anisidine and 4-chloroaniline were found ubiquitously in sediments. Aniline and 4-CA accounted for over 65% of the total AAs concentrations. Sediments from a wastewater lagoon contained the highest concentrations of AAs and nicotine suggesting that sewage discharges are a major source of these chemicals in the aquatic environment. The risk quotients calculated for the chemicals in sediments suggested potential threat to aquatic organisms, especially from nicotine contamination. However, it should be noted that samples analyzed in the study were collected over a broad time period and stored in the laboratory for several years prior to analysis. Therefore potential volatilization loss of AAs cannot be ignored. Nevertheless, our results provide baseline information on the occurrence of AAs and nicotine in aquatic ecosystems and their environmental risks.

Supplementary Material

Supporting Information

Highlights.

  1. Aromatic amines (AAs) and nicotine were measured in sediments from US waterbodies

  2. Seven of the14 AAs analyzed were found frequently, with aniline predominating

  3. Concentrations of AAs were in the range of 10.2 – 3140 ng/g dry wt

  4. Highest concentrations AAs and nicotine were found in wastewater lagoon

  5. Nicotine followed by 4-chloroaniline exhibited the highest risk quotients

Acknowledgments

The study was funded by the US National Institute of Environmental Health Sciences (NIEHS) under award number U2CES026542 (KK), the Polish-US Fulbright Commission with the Fulbright Senior Award 2021/22 grant (PL/2021/54/SR) (MU), and NIEHS award P42ES013661 (KCH). The content is solely the responsibility of the authors and does not necessarily represent the official views of the NIEHS and Polish-US Fulbright Commission.

Footnotes

CRediT authorship contribution statement

MU: Data curation, Formal analysis, Writing - original draft. SC: Methodology, Sample analysis, Manuscript review. AM: Samples, Manuscript review; KCH: Samples, Manuscript review; KK: Conceptualization, Funding acquisition, Supervision, Writing - review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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