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Article

An Interdisciplinary Assessment of the Impact of Emerging Contaminants on Groundwater from Wastewater Containing Disodium EDTA

by
Laura Ducci
,
Pietro Rizzo
*,
Riccardo Pinardi
* and
Fulvio Celico
Department of Chemistry, Life Sciences and Environmental Sustainability, University of Parma, Parco Area delle Scienze 157/A, 43124 Parma, Italy
*
Authors to whom correspondence should be addressed.
Sustainability 2024, 16(19), 8624; https://doi.org/10.3390/su16198624
Submission received: 4 August 2024 / Revised: 29 September 2024 / Accepted: 2 October 2024 / Published: 4 October 2024
(This article belongs to the Section Waste and Recycling)
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Abstract

:
In recent years, there has been a surge in interest concerning emerging contaminants, also known as contaminants of emerging concern (CECs), due to their presence in environmental matrices. Despite lacking regulation, these chemicals pose potential health and environmental safety risks. Disodium EDTA, a widely utilized chelating agent, has raised concerns regarding its environmental impact. The present work aimed to verify the presence of Disodium EDTA at the exit of eight wastewater treatment plants discharging into some losing streams flowing within a large alluvial aquifer. Conducted in the Province of Parma (Northern Italy), the research employs a multidisciplinary approach, incorporating geological, hydrogeological, chemical, and microbial community analyses. Following a territorial analysis to assess industries in the region, through the use of ATECO codes (a classification system for economic activities), the study investigated the concentration of Disodium EDTA in effluents from eight diverse wastewater treatment plants, noting that all discharges originate from an activated sludge treatment plant, released into surface water courses feeding the alluvial aquifer. Results revealed detectable levels of Disodium EDTA in all samples, indicating its persistence post-treatment. Concentrations ranged from 80 to 980 µg/L, highlighting the need for further research on its environmental fate and potential mitigation strategies. Additionally, the microbial communities naturally occurring in shallow groundwater were analyzed from a hydrogeological perspective. The widespread presence of a bacterial community predominantly composed of aerobic bacteria further confirmed that the studied aquifer is diffusely unconfined or semi-confined and/or diffusely fed by surface water sources. Furthermore, the presence of fecal bacteria served as a marker of diffuse leakage from sewage networks, which contain pre-treated wastewater. Although concentrations of Disodium EDTA above the instrumental quantification limit have not been found in groundwater to date, this research highlights the significant vulnerability of aquifers to Disodium EDTA. It reveals the critical link between surface waters, which receive treated wastewaters impacted by Disodium EDTA, and groundwater, emphasizing how this connection can expose aquifers to potential contamination. At this stage of the research, dilution of wastewaters in surface- and groundwater, as well as hydrodynamic dispersion within the alluvial aquifer, seem to be the main factors influencing the decrease in Disodium EDTA concentration in the subsurface below the actual quantification limit. Consequently, there is a pressing need to enhance methodologies to lower the instrumental quantification limit within aqueous matrices. In a broader context, urgent measures are needed to address the risk of diffuse transport of CECs contaminants like Disodium EDTA and safeguard the integrity of surface and groundwater resources, which are essential for sustaining ecosystems and human health.

1. Introduction

Between the 1960s and 1970s, the adverse effects of some new synthetic chemical products on the environment and human health became apparent soon after their synthesis and subsequent widespread release into environmental matrices. Among the most significant examples are organic pollutants (POPs), including organochlorine pesticides such as dichlorodiphenyltrichloroethane, commonly known as DDT, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) [1]. This scenario has, therefore, highly influenced legislation and the assessment of the impact of chemical pollution substances that are subject to monitoring for environmental protection and safeguarding.
In recent decades, there has also been a growing interest in the study and research into environmental matrices of new chemical substances that are not included in current environmental legislation and regulatory programs. These chemicals, known as contaminants of emerging concern (CECs), are not yet regulated under current environmental regulations or laws but are found in numerous and spread environmental matrices, such as rivers [2,3,4,5], lakes [6], soils [7], wastewater [8,9,10], biosolids [11], and even groundwater bodies [12,13,14,15,16].
In particular, urban wastewater treatment plants (WWTPs) cannot remove CECs from sewage using conventional treatments [17,18], such as filtration [19], activated sludge [20,21], and disinfection [22]. Based on the above information, greener technologies are urgently needed to effectively remove these contaminants in wastewater treatment plants without negatively impacting the environment [23]. For this reason, wastewater plant effluents are also inferred as a source of these chemicals since an important fraction of them may be released into the aquatic environment through the effluents [24,25,26] and reach the aquifer through interaction with surface water courses, generating potential risks for public health and environmental safety. In addition to this, due to their direct exposure to anthropogenic impacts, surface waters are vulnerable to becoming important basins for these micropollutants [27,28,29,30,31,32]. This, on the one hand, entails adverse effects on both wildlife and humans [33,34,35], restraining the use of water for consumption, irrigation, and recreation purposes [31,36], and, on the other hand, can generate groundwater pollution, through the feeding of the aquifer by impacted surface water courses.
CECs include over 3000 types of compounds and their derivatives, such as pesticides, fertilizers, microplastics, heavy metals, pharmaceutical and personal care products (PPCPs), including fragrances, UV filters, insect repellents, and antimicrobials [37,38]. Concerning risks to human health, CECs can harm human health and wildlife, resulting in reproductive and endocrinal disabilities [39,40]. The EU Water Framework Directive (WFD) was created in 2000 to avoid additional deterioration of the water status. The WFD specifies regulatory measures to prevent the deterioration of the ecological and chemical status of water bodies within the European Union [41]. Since 2000, it has been Europe’s leading law for water protection. It applies to inland, transitional, and coastal surface waters and groundwater and aims to achieve a good chemical status for all water bodies [41]. The WFD has given significant impetus in this direction, but achieving objectives for the protection of water resources involves the development of complex policies. It is necessary to affect a heterogeneous set of phenomena that compromise the ecological water status, adopting a multidisciplinary method through a holistic approach, which guarantees an accurate overview of the problem. The European Commission, to improve the application and implementation of chemical monitoring programs by the Member States, established in 2010 an expert group, the Chemical Monitoring and Emerging Pollutants (CMEP), to deepen the scope of emerging pollutants, including analytical methods, information on hazards, levels in the environment and patterns of use [42].
Although the knowledge about their environmental concentrations and fate is still mostly unknown, some of these CECs have the potential for bioaccumulation and/or are bioactive substances that may compromise living organisms. For example, some UV filters, such as 4-methylbenzylidene camphor (4-MBC), are suspected of presenting estrogenic activity [39].
Within this ongoing research, Ducci et al. [43] detected the presence of Disodium EDTA at the inlet of a wastewater treatment plant in Italy, while this was not detected in the groundwater. Disodium EDTA (CAS: 139-33-3), also known as sodium ethylenediaminetetraacetate, is a widely used chemical compound in various sectors due to its chelating properties and ability to bind metal ions. Disodium EDTA has the chemical formula C10H14N2Na2O8 and features a complex molecular structure. It is a polyaminocarboxylic acid renowned for its capacity to form stable complexes with metal ions, particularly heavy metal ions like calcium and magnesium. Its water solubility contributes to its versatility in various applications. Disodium EDTA finds applications in several sectors, including (i) the food industry (it is used as a chelating agent to prevent food oxidation and improve the stability of food colorants), (ii) cosmetics and personal care products (it stabilizes products like creams and lotions, preventing the formation of undesired precipitates), and (iii) the pharmaceutical industry (it is employed as a chelating agent in pharmaceutical formulations to enhance drug stability).
Despite its numerous uses, Disodium EDTA has raised concerns regarding its potential environmental impact. As described in the previous lines, the advantage of using Disodium EDTA in different industrial contexts is due to its ability to chelate heavy metals, which predisposes this chemical to assist the conservation and stabilization activities of certain products. At the same time, the possible presence of this substance in environmental matrices could lead to the mobilization and dispersion of heavy metals in soil and water systems, potentially damaging ecosystems and human health.
The present work aimed to verify the presence of Disodium EDTA at the exit of eight wastewater treatment plants discharging into some losing streams flowing within a large alluvial aquifer. The choice of analyzing wastewaters instead of groundwater in terms of Disodium EDTA concentrations is because the current chemical analyses still have high detection limits that do not allow the detection of this compound in saturated aquifers to date [43]. From this perspective, the link between wastewater treatment plants and groundwater was obtained by analyzing the aquifer properties in detail from a hydraulic point of view. The autochthonous microbial community in groundwater was also characterized in order to check the existence of possible natural attenuation. Microbial communities were also used as natural tracers to refine knowledge about local hydrodynamic processes and interaction between surface and groundwater.

2. Study Area

The Po Valley is largely the most urbanized and industrialized area in the Italian peninsula, and the possible sources of Disodium EDTA contamination are numerous and widespread. The research was carried out in different geographic and geologic contexts of Parma province, partly placed in the Northern Apennine valley floor, on the south, and partly in the Parma plain to the North, both located in this highly industrialized sector of Italy (Figure 1).
In the valley floor contexts (LDCA and LDLA wastewater treatment plants), the geological unit is deposited to the sides of the current riverbeds by composing small intravalley plains, covering the Apennine bedrock with thicknesses less than 10 m and characterized with very coarse lithologies (gravel in prevalence). In the plain (LDTR, LDCO, LDFE, LDPA, LDFO, and LDME wastewater treatment plants), the same geological unit consists of several hundred meters thick of alternating fine (silts and clays) and coarse (gravels and sands) layers resulting from the alluvial dynamics of the Apennine rivers and streams that filled the basin (Figure 1).
From a hydrogeological point of view, groundwater flows in this unit according to the topographic gradient from S–SE to N–NE [44]. The hydrogeologic macro asset can be defined as a multilayer aquifer where the highest permeability bodies consist of gravels and sands (hydraulic conductivity varying from 1.2 × 10−5 to 4.9 × 10−5 m/s from Zanini et al. [45]) with decreasing grain size toward the north, and silty–clayey interposed aquitards (hydraulic conductivity varying from 9.3 × 10−9 to 1.3 × 10−7 m/s from Zanini et al. [45]). As demonstrated by Ducci et al. [43], locally, these aquitards do not have sufficiently low permeability to allow total hydraulic isolation of the different high-permeability bodies. At the bottom of the entire system, Pliocene clays are considered as a regional-scale diffuse aquiclude. The hydraulic relationships between the aquifer and surface water courses have been investigated for specific tracts of several streams in the Parma Plain area [46,47], also through isotopic investigations, confirming the existence of losing streams [48]. The interaction between surface and groundwater was further analyzed at the site scale in the present work. In some cases, the sedimentary geometries of river or stream incisions that deposit coarser sediments (known as channel belt geometry, see Amorosi et al. [49] and Bruno et al. [50]) could be able to hydraulically connect the surface and the underlying aquifers; on the contrary, where riverbeds stand over continuous fine deposits bodies, the direct connection is absent or inconsiderable.
The hydraulic heterogeneity of aquifer bodies in the plain can lead to the presence of local barriers in groundwater flow proceeding downstream. This setting could cause the outcrop of groundwater originating the known “fontanili” and “risorgive” (e.g., [51,52]), which has also been the subject of analysis in the present work (Figure 1). From the ecological point of view, the risorgive or fontanili are small, semi-artificial, aquatic ecosystems (see Kløve et al. [53]) that are usually detected within the Po River Basin, the largest watershed in Italy (more than 70,000 km2).
The test area is a built environment with several agricultural (intensive models prevailing; e.g., [54]) and industrial activities, the latest dominated by the following sectors (i) agro-alimentary; (ii) production of food machinery, preservation equipment, machines, and packaging; (iii) pharmaceuticals and perfumery; and (iv) personal care and well-being [55].
Due to the human activities described above, different kinds of contamination were already detected and studied within the shallow aquifer system. Agricultural pressures cause widespread nitrate contamination of groundwater and groundwater-dependent ecosystems (GDEs) in the study area (e.g., [51,56]), as well as within the wider Po plain (e.g., [57,58,59,60,61,62]). Differently, urban and industrial activities were linked to microplastics [47], chlorinated solvents [45,46,63], fecal matter, and personal care products [43,64].

3. Materials and Methods

3.1. Geological Elaborations

Considering that Disodium EDTA discharges flow into local canals, streams, and rivers, the relationship between watercourses and aquifer bodies assumes high importance in understanding the possible infiltration of this substance into groundwater. For this purpose, ten hydrogeological sections orthogonal to the riverbed were designed and constructed downstream of each wastewater treatment plant’s release point. The geological and stratigraphic data on which these reconstructions were derived from the scientific literature [44] and subsurface investigation (by ISPRA and Emilia-Romagna Region boreholes public databases). The elaboration focused on reconstructing the physical (and consequently hydraulic) connection between the existing incisions of the surface runoff reticulum and the aquifer layers in the first tens of meters of the subsurface. The piezometric level refers to the shallow aquifer layer and was included based on the groundwater flow net reported in [44].

3.2. Examination of Productive Activities in the Territory of Parma

A preliminary examination of productive activities, identified by the ATECO (short for ‘ATtività ECOnomiche’, an Italian classification system for economic activities) code, was conducted within the territory of the Province of Parma. The ATECO code consists of an alphanumeric sequence designed to identify a specific economic activity. In this sequence, the letters in the code delineate the macroeconomic sector, while the numbers, ranging from two to six digits, provide details at various levels, specifying the articulations and subcategories within the sectors themselves. ATECO serves as the classification system for economic activities in Italy and is used by ISTAT (in Italian: Istituto Nazionale di Statistica) for statistical purposes in collaboration with other institutions, ministries, and business associations involved in statistics. This assessment aimed to determine which business activities could be involved in the use of Disodium EDTA, considering the substance’s specified applications in the current regulations of the European territory.

3.3. Wastewater Discharge Selection and Sampling

Following the identification of companies potentially involved in the use of Disodium EDTA, the next step involved selecting eight wastewater treatment plants in Parma territory to sample their effluents.
To diversify the types of sampled discharges, the selection parameters for wastewater treatment plants to be characterized were: (i) plant capacity expressed with (a) the average daily volume of treated effluents (m3/d) and (b) the population equivalent units, (ii) the number of inhabitants in the municipality where the plant is located (from ISTAT database), (iii) the number of industrial activities discharging into the wastewater treatment plant, and (iv) the number of industrial activities potentially involved in the use of Disodium EDTA discharging into the wastewater treatment plant while maintaining the fact that all discharges originate from an activated sludge treatment plant, released into surface water courses flowing within the alluvial aquifer. Among the eight plants, two were selected to analyze the potential impact (in terms of Disodium EDTA) of the only civil wastewater since the industrial wastewater treated at the same plants originates from industrial activities that do not utilize the studied emerging contaminant.
To ensure the comparability of the analytical results and minimize the dilution due to surface runoff, wastewaters were simultaneously sampled in each of the eight plants through 24 h composite sampling on the same day in April 2023, during a prolonged no-rain period.

3.4. Chemical Analysis

In accordance with other authors (e.g., [43,65]), wastewater sample collection took place once in April 2023, during dry weather conditions (defined as no rain in the previous 24 h and <2 mm in the previous 48 h [66]).
Water samples were collected from eight wastewater treatment plants in Parma. The selection of these plants is based on the ATECO code for recognizing which business activities could be involved in the use of disodium EDTA.
All wastewater samples (250 mL) were collected in amber glass bottles, stored in a refrigerated box, and transported to the laboratory.
The analyses were performed at Analytice s.a.r.l. (société à responsabilité limitée), a laboratory with ISO 17025 [67] accreditation recognized by the French Accreditation Committee (ILAC full members). In particular, gas chromatography combined with mass spectrometry (GC/MS) was performed to analyze Disodium EDTA. Samples were analyzed versus EDTA, and values were then calculated into Disodium EDTA. The samples were analyzed according to EN ISO 16588 [68]. The samples were derivatized with isopropanol/acetylchlorid and extracted with hexane. The extracts were then injected using gas chromatography (column DB-XLB) coupled to a mass spectrometer detector (GC-MS).

3.5. Next-Generation Sequencing (NGS) for Bacterial Community Analyses

According to several authors (e.g., [69,70,71,72,73,74,75,76]), molecular approaches can help understand hydrogeological settings and dynamics. With this aim, the present study employed next-generation sequencing (NGS) techniques to analyze microbial communities naturally occurring in shallow groundwater and use them as indicators of surface–ground-water interactions and markers of diffuse leakage from sewage networks. Groundwater was sampled from 11 piezometers (Pz1S, Pz2S, Pz3S, Pz4S, Pz3A, Pz4A, Pz5A, Pz6A, Pz7A, Pz8A, Pz3C; Figure 1), and 3 springs (LDF1, LDF2, LDS1; Figure 1).
These groundwater sample points were selected based on their interception of the shallow aquifer, which is directly fed from surface watercourses flowing into the unconfined portion of the aquifer, rendering it the most susceptible to contamination from Disodium EDTA. In particular, the area depicted in Figure 1 includes 11 piezometers drilled to depths ranging from 20 to 27 m and screened within the shallowest gravel and sand layer.
Groundwater samples (2 L) were passed through sterile mixed esters of cellulose filters (S-PakTM Membrane Filters, 47 mm diameter, 0.22 μm pore size, Millipore Corporation, Billerica, MA, USA) within 24 h of collection. Bacterial DNA extraction from these filters was executed using the commercial FastDNA SPIN Kit for soil (MP Biomedicals, LLC, Solon, OH, USA) along with the FastPrep® Instrument (MP Biomedicals, LLC, Solon, OH, USA). Post-extraction, DNA integrity and quantity were assessed via electrophoresis in 0.8% agarose gel containing 1 μg/mL of Gel-RedTM (Biotium, Inc., Fremont, CA, USA). The bacterial community profiles in the samples were then generated using next-generation sequencing (NGS) technologies at the Genprobio Srl Laboratory, adhering to the protocol outlined by Ducci et al. [64].

4. Results

4.1. Hydrogeological Model

Starting from the south, in the intravalley lowland (LDCA and LDLA wastewater treatment plants), groundwater flows within the unconfined coarse deposits according to the topographic gradient. Recharge, in addition to local precipitation, could derive from the Apennine aquifers located on the valley slopes and from the Baganza and Parma streams waterflow. The presence of fine sediment in or on top of the most superficial aquifer is so minimal as never to support shallow groundwater confinement conditions. Low permeability rock units (turbidites) or aquiclude marly-clay units can be found at the base of the alluvial gravel aquifer, as well as the edges (sections aa’ and bb’ in Figure 2).
In the foothill fluvial terracing contexts (LDTR, LDFE, and LDCO wastewater treatment plants), groundwater flows under unconfined conditions and within an aquifer in hydraulic continuity with the riverbeds, respectively, of Termina Stream, Cinghio Stream, Manubiola Stream, and Taro River. In these cases, the frequent top lap stratigraphic geometries (see Mitchum [77]) of the higher-permeability strata could facilitate the downflow of groundwater and, consequently, of the released substance to the deeper portion of the multilayer aquifer (sections cc’, dd’, ee’, gg’ and ff’ in Figure 2).
Proceeding to the north, toward the plain (location of the remaining wastewater treatment plants and sampling points shown in Figure 1), an increase in thickness and frequency of the finer layers is known to promote confinement of the more superficial aquifer; however, this condition may disappear where the integrity of aquitards is disrupted by the incision of current riverbeds or their past record. Recharge derives mostly from upstream and from losing riverbeds. Down valley to all the analyzed wastewater treatment plant’s release points, this condition has been verified from the hydrogeological setting to result in the correspondence of Recchio, Parma, and Parmetta streams (sections hh’, ii’ and mm’ in Figure 2).
All the reconstructed scenarios show frequent interaction relationships between surface water and groundwater despite the substantial difference in geographical and geological location of the analyzed sections (Figure 2). Therefore, canals, rivers, streams, and their riverbeds composed mainly of highly permeable sediments (sand and gravel) diffusely favor the migration of Disodium EDTA towards the groundwater within the whole study area.
The hydrogeological findings provide a crucial understanding of the aquifer’s vulnerability and its interaction with surface water, establishing the foundation for the subsequent examination of industrial activities in the region (see paragraph below 4.2).

4.2. Productive Activities and Wastewater Treatment Plants

In the study area, there are a total of 316 industrial activities that collectively impact the 8 selected wastewater treatment plants, and among them, 25 may use Disodium EDTA. Industrial activities attributed to the use of Disodium EDTA fall within the following production categories (ATECO): (i) production of ready meals and dishes from other food products, (ii) manufacture of basic pharmaceutical products, (iii) manufacture of toiletry products: perfumes, cosmetics, soaps, and similar items, (iv) production of other food products not elsewhere classified (n.e.c.), and (v) packaging and wrapping of food products (see Table 1) [78,79].
Diverse features characterize the eight selected wastewater treatment plants. The range of average daily volume varies from a minimum of 450 to a maximum of 24,000 (m3/d). The population equivalent units range from a minimum of 4000 to a maximum of 168,000, while the number of inhabitants ranges from a minimum of 2062 to a maximum of 100,015 citizens. Table 2 summarizes the most significant characteristics of each plant, including the total number of industrial activities that discharge effluents into the individual wastewater treatment plant and those attributed to the use of Disodium EDTA.
The preliminary assessment of industrial activities using ATECO codes allowed for the identification of potential sources of Disodium EDTA, justifying the selection of effluent samples from the associated treatment plants, whose discharges are released into portions of the aquifer where interaction has been confirmed, as discussed in Section 4.1.

4.3. Chemical Results

Disodium EDTA was detected in all wastewater samples collected within the present study, with concentrations ranging from 80 to 980 µg/L and an average value of 343 µg/L (Table 3).
The chemical analysis confirms detectable levels of Disodium EDTA in the sampled effluents, illustrating its persistence after the treatment and potential impact on the aquifer.

4.4. Biomolecular Investigations

The MiSeq sequencing runs produced an average of 55,033 sequences for the samples collected at piezometer Pz1S, Pz2S, Pz3S, Pz4S, PZ3A, Pz4A, Pz5A, Pz6A, Pz7A, Pz8A, and Pz3C. It should be noted that the final read number reported for the Pz3C point fell below 30,000 (refer to Table 4), which may not be sufficiently high for a thorough examination of the microbial community. Regarding spring samples, the amount of DNA extracted was so low that the PCR failed and did not allow the microbial community analysis to be performed.
The 16S rRNA gene sequences generated in this study have been archived in the NCBI Sequence Read Archive under accession number PRJNA1117376.
The analysis of the groundwater microbial community revealed a high degree of heterogeneity.
Proteobacteria, Bacteroidetes, Firmicutes, and Actinobacteria, accounting for average values ranging from 9.21% to 55.31%, were the four major phyla in the groundwater samples. Proteobacteria was the dominant phylum in most samples, except for Pz4A, where Bacteroidetes was the most abundant phylum (51.11%), while for Pz6A and Pz8A, the highest concentrations were achieved by Firmicutes, with concentrations of 40.41% and 50.39%, respectively.
The most abundant families in groundwater samples were Burkholderiaceae, Comamonadaceae, Sphingomonadaceae, Flavobacteriaceae, Lachnospiraceae, Oxalobacteraceae, Xanthomonadaceae, and Acetobacteraceae, with a range of average abundance between 1.97% and 8.26%. The Burkholderiaceae family shows significant variation in abundance levels across the different sampling points. At the Pz1S, Pz2S, Pz3S, and Pz4S points, the abundance was, respectively, 23.91%, 21.67%, 20.13%, and 13.31%. However, this abundance decreased significantly at Pz3A, Pz4A, Pz5A, Pz6A, Pz7A, and Pz8A, ranging between 0.11% and 1.50%. A similar trend can be observed for the Sphingomonadaceae family, with abundance ranging from 13.77% to 18.03% at Pz2S, Pz3S, and Pz4S. The abundance was minimal in the remaining sampling points, ranging from 0.17% to 2.75%. The families Xanthomonadaceae and Acetobacteraceae exhibited significant presence exclusively at Pz1S, with values of 20.90% and17.72%, respectively, while in the remaining sampling points, the abundance oscillated between 0.03% and 1.13%. The Flavobacteriaceae family was particularly abundant at the Pz4A and Pz4S points, with 45.39% and 6.32%, respectively. The abundance was very low in the remaining sampling points, ranging from 0.06% to 1.23%. The Comamonadaceae family showed significant abundance at sampling points Pz3A, Pz4A, Pz5A, and Pz7A, with percentages ranging from 3.12% to 27.75%. Lachnospiraceae dominated at Pz6A and Pz8A with concentrations of 15.07% and 19.91%; Oxalobacteraceae dominated at Pz7A with 23.03%, while the concentration was strongly limited at the other points.
At the genus level, the most abundant bacteria found in all groundwater samples were Flavobacterium, Limnohabitans, Novosphingobium, Pseudomonas, Hydrogenophaga, Herminiimonas, Silanimonas, and Roseococcus; the concentrations averaged between 1.82% and 5.46%. In particular, the average prevalence of each bacterial genus provides an overview of the distribution of bacterial genera across the entire dataset of this study; however, each sample has a unique bacterial composition, with a distinct combination of dominant bacterial genera (Table 5). Various bacterial genera are more prevalent than others in different samples, indicating significant variations in their prevalence among the different samples. For example, it can be observed that sample Pz4A is mainly composed of Flavobacterium at 44.74%, while Limnohabitans is the predominant genus at 22.31% in sample Pz7A and Hydrogenophaga in Pz1S, with a concentration of 22.01%.
To sum up, the groundwater community is significantly heterogeneous; however, it is emphasized that, at the lower level, the shallow aquifer is characterized by a bacterial community predominantly composed of Gram-negative, aerobic, chemoorganotrophic bacteria, with wide ranges of growth such as Flavobacterium [80], Limnohabitans [81], Novosphingobium [82], Pseudomonas [83], and Hydrogenophaga [84]. Furthermore, it is noteworthy that among the top 3 abundant genera detected in Pz5A, Pz6A, and Pz8A, bacterial genera belong to the mammalian intestinal microbiome (e.g., Bacteroides, Escherichia-Shigella, Bifidobacterium, Lactobacillus, and Faecalibaculum) [85,86,87,88,89].
The dominance of aerobes confirms that the studied aquifer is diffusely unconfined or semi-confined and/or diffusely fed by surface water courses. Additionally, the presence of fecal bacteria indicates diffuse leakage from sewage networks, which contain pre-treated wastewater and, consequently, Disodium EDTA [43]. These data confirm further vulnerability for the shallow aquifer; in addition to its interaction with surface waters, losses from the sewage system, including Disodium EDTA, can potentially impact groundwater quality [43].
From the perspective of potential genera capable of degrading Disodium EDTA, organisms including representatives of the genera Methylobacterium, Variovorax, and Bacillus were isolated through the use of a mixed culture utilizing EDTA as the sole carbon source from an effluent treatment plant [90]. In the analyzed samples, the genus Methylobacterium was detected in groundwater samples Pz3A, Pz5A, Pz6A, Pz7A, Pz8A, Pz2S, Pz3S and Pz4S with an average of 0.19%. Additionally, the genus Variovorax was found with an average concentration of 0.20% in Pz3A, Pz4A, Pz5A, Pz6A, Pz7A, Pz8A, Pz2S, Pz3S and Pz4S, while Bacillus was found in Pz3A, Pz4A, Pz5A, Pz6A, Pz7A, Pz8A and Pz3S with a concentration of 0.27%. These data show that, based on the literature available so far, the bacterial community is not significantly characterized by microorganisms with degradative potential for Disodium EDTA.

5. Discussion

In summary, this study highlights the critical importance of interdisciplinarity in understanding and managing the potential contamination of groundwater by Disodium EDTA and, more widely, of CECs. The combined analysis of the aquifer’s hydraulic properties and the autochthonous microbial community provided valuable insights into local hydrodynamic processes and the interaction between surface water bodies, where Disodium-EDTA-impacted effluents are discharged, and groundwater. This integrated approach offers a more comprehensive and refined assessment of contamination risks, as current detection techniques for groundwater are still not sensitive enough to directly identify this compound in aquifers [43].
The incapacity of water treatment plants to remove chemicals from the class of CECs [17,18] endangers surface water and poses a significant threat to groundwater quality [91,92,93]. In areas where surface and groundwater interact, such as the study area in this research, wastewater pollutants can contaminate aquifers.
In this specific case, the study area is characterized by high industrial activity, totaling 316 industrial activities. Of these, 25 may use Disodium EDTA. The daily volume of wastewater varies widely between different plants, ranging from 450 to 40,000 (m3/d). Population equivalent units fluctuate between 4000 and 180,000, while the population residing in the area ranges from 2062 to 100,015 inhabitants. Within this heavily industrialized area, the aim of this study was to diversify, as much as possible, the wastewater treatment plants from which effluents were sampled while keeping constant the fact that discharges were released into portions of the unconfined aquifer, which, through dispersion, feeds the underlying shallow aquifer. The risk of contamination from wastewater in the study area is confirmed by the detection of Disodium EDTA in all wastewater samples collected within the present study, with concentrations ranging from 80 to 980 µg/L, with an average value of 348 µg/L. In particular, as shown in Figure 3, no association was found between the number of industries potentially using Disodium EDTA, according to the ATECO code, discharging wastewater into each treatment plant and the concentration of Disodium EDTA detected in the plant’s effluents. Despite variations in the presence of industries utilizing Disodium EDTA among different treatment plants, the concentrations of the substance fluctuate without a discernible pattern. For example, LDPO, with eight industries using Disodium EDTA, exhibits concentrations of 270 µg/L, while LDTR, with only two industries utilizing Disodium EDTA, records the highest concentration of 980 µg/L. LDCA and LDME, which have no industries using Disodium EDTA, show overlapping concentrations of 83 µg/L and 80 µg/L, respectively. Furthermore, considering the characteristics of the plants in terms of size and treated volumes, this lack of direct association is emphasized, challenging conventional assumptions and highlighting the need for further research to clarify the complex factors influencing the presence of Disodium EDTA in wastewater treatment plants. Additionally, the overlapping concentrations between LDCO and LDME suggest the possibility of “background contamination” from domestic effluents [94].
However, despite (a) the widespread detection of Disodium EDTA in wastewaters, (b) the hydraulic interconnection between surface- and groundwater, and (c) the losses from the sewage system, Disodium EDTA has never been detected in the studied groundwater [43]. This result can be due to one or more of the following factors: (i) the relatively high quantification limit of the available analytical techniques; (ii) the dilution of Disodium EDTA, also due to hydrodynamic dispersion within the aquifer system; and (iii) the possible microbial natural attenuation (Figure 4).
The results of the microbial community suggest that the vulnerability of the shallow aquifer remains high, as evidenced by the presence of aerobic bacteria that confirm the aquifer is diffusely unconfined or semi-confined and/or widely fed by surface water courses, along with the presence of genera belonging to the mammalian intestinal microbiome, indicating leaks from sewer networks. Both of these factors expose the shallow aquifer to pollution from Disodium EDTA, highlighting its vulnerability; on the one hand, through effective infiltration from surface water bodies impacted by contaminated effluents, and, on the other hand, through leaks from sewage systems [43] (as shown in Figure 4). Furthermore, although some microbial genera with potential degradative capabilities for EDTA, such as Methylobacterium, Variovorax, and Bacillus, have been detected in groundwater, their concentrations appear to be low, suggesting that the possible contribution of biodegradation to the fate of Disodium EDTA in the studied aquifer is limited. It is important to note that this assessment of low capacity is exclusively based on bacteria whose physiology is known and for which the degradative potential towards compounds like EDTA has been tested; in particular, for uncultured organisms, their degradative capabilities are unknown, and they represent a significant portion of the microbial community in the analyzed samples, with percentages ranging from 3.63% to 49.70%, and an average of 20.40%.

6. Conclusions

In conclusion, the findings of this study highlight the significant challenges posed by the presence of Disodium EDTA in wastewater and its potential impact on both surface water and groundwater quality. The inability of conventional water treatment plants to effectively remove such chemicals increases the risk of contamination, particularly in regions characterized by high industrial activity, including those involved in food production and packaging as well as PPCPs production. Despite the absence of detectable levels of Disodium EDTA in groundwater thus far, the hydrogeological dynamics elucidated in this interdisciplinary research underscore the interconnectivity of surface and subsurface water systems, thereby expanding the scope of potential environmental repercussions. Consequently, there is a pressing need to enhance methodologies to lower the instrumental quantification limit within aqueous matrices. In a broader context, urgent measures are needed to address the risk of diffuse transport of CECs contaminants like Disodium EDTA and safeguard the integrity of surface and groundwater resources, which are essential for sustaining ecosystems and human health.

Author Contributions

Conceptualization, L.D., P.R. and F.C.; methodology, L.D. and P.R.; software, R.P.; validation F.C.; formal analysis, L.D., P.R., R.P. and F.C.; investigation, L.D, R.P. and P.R.; resources, F.C.; data curation, L.D., P.R. and R.P.; writing—original draft preparation, L.D. and R.P.; writing—review and editing, L.D., P.R., R.P. and F.C.; visualization, L.D., P.R. and R.P.; supervision F.C.; project administration, F.C.; funding acquisition, F.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

The relevant data can be found as follows: “Regione Emilia Romagna boreholes public Database” at https://servizimoka.regione.emilia-romagna.it/mokaApp/apps/geg/index.html (accessed on 30 May 2024); “ISPRA boreholes public Database” at https://www.isprambiente.gov.it/it/banche-dati/banche-dati-folder/suolo-e-territorio/dati-geognostici-e-geofisici (accessed on 30 May 2024).

Acknowledgments

We acknowledge IRETI S.p.A. for the information and access to wastewater sampling.This research benefited from the equipment and framework of the COMP-R Initiative, funded by the “Departments of Excellence” program of the Italian Ministry for University and Research (MUR, 2023–2027). We are grateful to the reviewers for their constructive comments and valuable suggestions.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. Hydrogeological map (the hydrogeological sections are shown in Figure 2).
Figure 1. Hydrogeological map (the hydrogeological sections are shown in Figure 2).
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Figure 2. Hydrogeological sections (section traces are shown in Figure 1).
Figure 2. Hydrogeological sections (section traces are shown in Figure 1).
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Figure 3. Comparison between the number of industries potentially using Disodium EDTA and the concentration of Disodium EDTA in wastewater effluents. The bar chart (black bars) represents the number of industrial activities categorized by the ATECO code that can use Disodium EDTA. The line graph (blue line) shows the concentration of Disodium EDTA (µg/L) detected in the effluents of each corresponding treatment plants.
Figure 3. Comparison between the number of industries potentially using Disodium EDTA and the concentration of Disodium EDTA in wastewater effluents. The bar chart (black bars) represents the number of industrial activities categorized by the ATECO code that can use Disodium EDTA. The line graph (blue line) shows the concentration of Disodium EDTA (µg/L) detected in the effluents of each corresponding treatment plants.
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Figure 4. Conceptual model.
Figure 4. Conceptual model.
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Table 1. Complete inventory of industrial activities in the study area that, according to the ATECO description of their production activities, could potentially use Disodium EDTA.
Table 1. Complete inventory of industrial activities in the study area that, according to the ATECO description of their production activities, could potentially use Disodium EDTA.
ATECO CodeATECO
Description of Economic Activities		Number of Industrial Activities
in the Study Area
10.85.09Production of ready meals and dishes from other food products7
21.10.00Manufacture of basic pharmaceutical products2
20.42.00Manufacture of toiletry products: perfumes, cosmetics, soaps, and similar items3
10.89.09Production of other food products not elsewhere classified (n.e.c.)2
82.92.10Packaging and wrapping of food products3
Table 2. Sampled wastewater treatment plant characteristics.
Table 2. Sampled wastewater treatment plant characteristics.
Plant Capacity
Wastewater Treatment PlantAverage Daily Volume (m3/d)Population Equivalent Units (n)Inhabitants
(n)		Industrial Activities
(n)		Industrial Activities that Can Use Disodium EDTA (n)
LDCA4504000206210
LDME4509600316840
LDCO300020,00014,711221
LDFE670050,0009168564
LDFO380016,0005543151
LDLA10,50025,00010,8011261
LDPO24,000168,000100,015618
LDTR180099009591312
Table 3. Results of Disodium EDTA analyses.
Table 3. Results of Disodium EDTA analyses.
SampleParameter
(CAS)		TechniqueAnalytical MethodDisodium EDTA
(µg/L)
LDCADisodium EDTA (139-33-3)GC-MSEN ISO 16588 [68]83
LDMEDisodium EDTA (139-33-3)GC-MSEN ISO 16588 [68]80
LDCODisodium EDTA (139-33-3)GC-MSEN ISO 16588 [68]340
LDFEDisodium EDTA (139-33-3)GC-MSEN ISO 16588 [68]350
LDFODisodium EDTA (139-33-3)GC-MSEN ISO 16588 [68]160
LDLADisodium EDTA (139-33-3)GC-MSEN ISO 16588 [68]480
LDPODisodium EDTA (139-33-3)GC-MSEN ISO 16588 [68] 270
LDTRDisodium EDTA (139-33-3)GC-MSEN ISO 16588 [68]980
Table 4. Number of 16S rDNA sequences obtained after NGS analysis.
Table 4. Number of 16S rDNA sequences obtained after NGS analysis.
Groundwater
Sample		Final Read Number
Pz1S45,846
Pz2S39,521
Pz3S54,855
Pz4S54,741
Pz3A69,745
Pz4A51,091
Pz5A77,817
Pz6A73,062
Pz7A59,631
Pz8A44,792
Pz3C23,600
Table 5. Percentage distribution of the top 3 bacterial genera for the different sampling points (Pz).
Table 5. Percentage distribution of the top 3 bacterial genera for the different sampling points (Pz).
Pz3A Pz4A Pz5A Pz6A Pz7A
Methylobacter5.03%Flavobacterium44.74%Pseudomonas6.75%Bacteroides8.15%Limnohabitans22.31%
Methylotenera4.68%Limnohabitans22.92%Lactobacillus3.97%Escherichia-Shigella6.06%Herminiimonas22.01%
Methylomonas4.46%Pseudarcicella4.28%Streptococcus2.90%Bifidobacterium3.61%Pseudomonas11.69%
Pz1S Pz2S Pz3S Pz4S Pz8S
Hydrogenophaga22.01%Novosphingobium12.14%Novosphingobium14.26%Novosphingobium8.00%Bacteroides7.21%
Silanimonas20.81%Azospirillum6.00%Limnohabitans5.17%Azospirillum7.47%Faecalibaculum6.88%
Roseococcus17.60%Sphaerotilus5.93%Sphingomonas3.60%Flavobacterium6.26%Lactobacillus6.57%
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Ducci, L.; Rizzo, P.; Pinardi, R.; Celico, F. An Interdisciplinary Assessment of the Impact of Emerging Contaminants on Groundwater from Wastewater Containing Disodium EDTA. Sustainability 2024, 16, 8624. https://doi.org/10.3390/su16198624

AMA Style

Ducci L, Rizzo P, Pinardi R, Celico F. An Interdisciplinary Assessment of the Impact of Emerging Contaminants on Groundwater from Wastewater Containing Disodium EDTA. Sustainability. 2024; 16(19):8624. https://doi.org/10.3390/su16198624

Chicago/Turabian Style

Ducci, Laura, Pietro Rizzo, Riccardo Pinardi, and Fulvio Celico. 2024. "An Interdisciplinary Assessment of the Impact of Emerging Contaminants on Groundwater from Wastewater Containing Disodium EDTA" Sustainability 16, no. 19: 8624. https://doi.org/10.3390/su16198624

APA Style

Ducci, L., Rizzo, P., Pinardi, R., & Celico, F. (2024). An Interdisciplinary Assessment of the Impact of Emerging Contaminants on Groundwater from Wastewater Containing Disodium EDTA. Sustainability, 16(19), 8624. https://doi.org/10.3390/su16198624

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