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Article

Recent Findings on the Pollution Levels in the Romanian Black


Sea Ecosystem: Implications for Achieving Good
Environmental Status (GES) Under the Marine Strategy
Framework Directive (Directive 2008/56/EC)
Andra Oros *, Valentina Coatu, Nicoleta Damir, Diana Danilov and Elena Ristea

Chemical Oceanography and Marine Pollution Department, National Institute for Marine Research and
Development (NIMRD) “Grigore Antipa”, 300 Mamaia Blvd., 900581 Constanta, Romania;
[email protected] (V.C.); [email protected] (N.D.); [email protected] (D.D.);
[email protected] (E.R.)
* Correspondence: [email protected]

Abstract: This study provides a comprehensive evaluation of contamination levels in the Romanian
Black Sea within the framework of the Marine Strategy Framework Directive (MSFD). Over the
course of five oceanographic expeditions between 2020 and 2022, data were gathered from 70 sta-
tions in transitional, coastal, shelf, and offshore waters of the Black Sea. Analyses were conducted
on water, sediment, and biota samples for key contaminants: heavy metals (HMs), polycyclic aro-
matic hydrocarbons (PAHs), and persistent organic pollutants (POPs) such as organochlorinated
pesticides (OCPs) and polychlorinated biphenyls (PCBs). The assessment identified contamination
hotspots near riverine inputs, urban runoff, harbor activities, and industrial discharges. Offshore
waters also showed measurable pollutant levels, likely from diffuse sources and atmospheric depo-
sition. The key findings reveal the widespread contamination of HMs, PAHs, and POPs across the
Romanian Black Sea, with concentrations in certain areas exceeding acceptable environmental
Citation: Oros, A.; Coatu, V.; Damir,
thresholds, highlighting ongoing challenges for regional pollution management. PAHs were prev-
N.; Danilov, D.; Ristea, E. Recent
alent in both nearshore and offshore regions, while OCPs and PCBs were detected across various
Findings on the Pollution Levels in
matrices, with significant concentrations observed in water and biota samples. The study empha-
the Romanian Black Sea Ecosystem:
Implications for Achieving Good
sizes the importance of integrated assessments within the MSFD framework, suggesting that future
Environmental Status (GES) Under evaluations should complement the “one out-all out” (OOAO) approach with multi-metric tools, to
the Marine Strategy Framework enhance the robustness of pollution status reporting. Despite improvements in some areas, contam-
Directive (Directive 2008/56/EC). ination remains a critical challenge, requiring strengthened regulations, improved waste manage-
Sustainability 2024, 16, 9785. ment, and increased regional cooperation to mitigate the ongoing risks to marine ecosystems. The
https://doi.org/10.3390/su16229785 findings provide valuable data for the upcoming national MSFD assessment cycle (2018–2023) and
Academic Editor: Tim Gray
highlight the need for sustained monitoring and coordinated efforts to ensure long-term marine
sustainability.
Received: 30 September 2024
Revised: 5 November 2024
Keywords: Black Sea; heavy metals; polycyclic aromatic hydrocarbons; organochlorinated
Accepted: 7 November 2024
pesticides; polychlorinated biphenyls; MSFD; GES; contamination status
Published: 9 November 2024

Copyright: © 2024 by the authors.


1. Introduction
Licensee MDPI, Basel, Switzerland.
This article is an open access article
Ocean pollution poses a significant risk to both global ecosystems and human well-
distributed under the terms and being, with contamination from industrial activities, agricultural runoff, and maritime
conditions of the Creative Commons transport leading to the degradation of marine environments. The Black Sea, a partially
Attribution (CC BY) license enclosed body of water surrounded by densely industrialized and populated regions, is
(https://creativecommons.org/license particularly vulnerable to these pressures [1–4]. This body of water is crucial to the re-
s/by/4.0/). gion’s fisheries, biodiversity, and tourism [5], but faces persistent pollution from riverine

Sustainability 2024, 16, 9785. https://doi.org/10.3390/su16229785 www.mdpi.com/journal/sustainability


Sustainability 2024, 16, 9785 2 of 49

inputs [6], urban runoff, and industrial discharges [7,8]. Ecological assessments revealed
that its ecosystem has undergone significant regime shifts, characterized by changes in its
structure and function, primarily attributed to pollution and overfishing [9–12]. The cu-
mulative effects of these contaminants not only endanger marine biodiversity but also
pose a serious health risk to humans who consume contaminated seafood [13].
Previous studies [14–21] report elevated hazardous substance levels across ecosystem
components; however, updated information for comprehensive regional assessments re-
mains limited, particularly within the context of the implementation of the European Ma-
rine Strategy Framework Directive (MSFD) [22,23]. This study addresses this knowledge
gap by providing an integrated assessment of contamination in the Romanian Black Sea,
including new data for offshore waters, which are not covered by regular monitoring, thus
contributing to ongoing efforts to achieve Good Environmental Status (GES) across Euro-
pean seas [22].
The Romanian Black Sea coast, facing distinct ecological and pollution pressures, is
significantly impacted by river discharge, urban and industrial runoff, and seasonal tour-
ism. Unlike widely studied open seas, the semi-enclosed Black Sea has distinct pollutant
retention and distribution patterns [24–26]. This study addresses the gaps in offshore data
with a focused analysis of contaminant distribution across the Romanian sector, providing
insights essential for region-specific management. Our approach distinguishes itself by
examining a broad spectrum of contaminants, including heavy metals (HMs), persistent
organic pollutants (POPs), and polycyclic aromatic hydrocarbons (PAHs). By analyzing
these pollutants across water, sediment, and biota, we achieve a comprehensive overview
of bioaccumulation and the ecosystem impact beyond typical single-matrix studies. To
enhance assessment reliability, we apply a multi-indicator evaluation approach that inte-
grates chemical and ecological indicators across multiple matrices. Using the One Out, All
Out (OOAO) principle with percentile-based metrics, our approach aligns with both the
Marine Strategy Framework Directive (MSFD) and Water Framework Directive (WFD).
This methodology, capturing cumulative impacts and subtle environmental risks, offers a
model for future monitoring in similar semi-enclosed marine systems.
The Marine Strategy Framework Directive (MSFD), formally known as Directive
2008/56/EC, was adopted by the European Union in 2008. Its main objective is to protect
the marine environment across Europe to achieve a Good Environmental Status (GES) in
EU marine waters by 2020 and to maintain it thereafter. The MSFD outlines an ecosystem-
based approach to managing human activities that affect the marine environment, focus-
ing on sustainable use while preventing further degradation. It establishes 11 descriptors
that member states must assess and manage to protect marine health, promote biodiver-
sity, and secure the resilience of marine ecosystems [22]. Good Environmental Status
(GES), defined within the Marine Strategy Framework Directive (MSFD, Directive
2008/56/EC), represents the environmental goal for EU marine waters. Achieving GES
means that the seas are ecologically diverse, clean, healthy, and productive, with their use
is sustainable, ensuring the ability of ecosystems to function fully and support human
needs. GES is assessed using 11 descriptors: biodiversity (D1), non-indigenous species
(D2), commercial fish and shellfish (D3), food webs (D4), eutrophication (D5), seafloor
integrity (D6), hydrographical conditions (D7), contaminants (D8), contaminants in sea-
food (D9), marine litter (D10), and energy, including underwater noise (D11); this is in
order to safeguard marine environments from significant human impact while promoting
sustainable use and resilience. Among them, Descriptor 8 focuses on pollutant status, en-
suring contaminants have no harmful impact on the ecosystem, while Descriptor 9 ad-
dresses the state of marine ecosystems with respect to seafood safety, ensuring contami-
nants do not significantly affect human health. These two descriptors are particularly rel-
evant for the Black Sea, given the historical and ongoing contamination issues in the re-
gion. Various hazardous substances have been documented to accumulate in the marine
environment, potentially leading to long-term ecological damage and health risks through
the food chain [27,28]. While the MSFD provides a general framework, the effectiveness
Sustainability 2024, 16, 9785 3 of 49

of its implementation varies across European regions. The Black Sea still faces substantial
challenges in monitoring, assessing, and managing pollution. The complexity of contam-
ination sources, coupled with the Black Sea’s semi-enclosed nature, exacerbates the diffi-
culty in mitigating these issues. Moreover, the region faces additional pressures from cli-
mate change, which can further influence contaminant distribution and impact [2,29,30].
The European Commission Decision 2017/848/EU, replacing Decision 2010/477/EU,
establishes criteria and methodological standards for the good environmental status
(GES) of marine waters, along with specifications and standard methods for monitoring
and assessment [31]. The Contaminants Expert Group, coordinated by the Joint Research
Centre (JRC), reviewed Descriptors 8 and 9. For Descriptor 8, the JRC recommends an EU-
wide list of elements for GES assessment based on the Water Framework Directive (WFD),
aligning GES thresholds with the WFD’s Environmental Quality Standards (EQSs). Na-
tional or regional criteria may be applied where EQSs are unavailable [32,33]. For De-
scriptor 9, the JRC suggests a similar list with GES thresholds based on the maximum
levels (MAC) for contaminants in food [34].
A 2021 JRC report reviewed the 2018 GES assessments from EU Member States, in-
cluding Romania [29,35]. It highlighted inconsistencies in the substances assessed, moni-
toring methods, and threshold values, especially in applying the WFD EQSs [31,32]. The
report calls for harmonized assessment methodologies, agreed threshold values, and en-
hanced regional coordination, particularly for offshore waters [35,36]. The JRC also noted
that many countries limit their Descriptor 9 assessments, which restricts understanding
of health risks. It recommends expanding the range of contaminants and improving re-
gional cooperation to align food safety standards [35]. To address discrepancies between
D8 and D9, the JRC emphasizes harmonization and coordinated monitoring efforts across
the EU to improve MSFD effectiveness [35].
Objectives of the study:
1. The quantification of hazardous substances concentrations across multiple environ-
mental matrices (water, sediment, and biota) in the Romanian Black Sea sector, cov-
ering transitional, coastal, shelf, and offshore areas.
2. The assessment of Good Environmental Status (GES): evaluate contamination levels
against the GES thresholds established under the MSFD, focusing on Descriptors 8
(pollution status) and 9 (seafood safety).
3. The identification of potential pollution sources, such as riverine inputs, industrial
discharges, urban runoff, and atmospheric deposition, based on spatial patterns of
contaminants in both nearshore and offshore areas.
4. The presentation of insights into the general effectiveness of the current regulatory
measures and pollution control efforts, and the provision of guidance on improving
monitoring and management strategies to better address marine contamination and
promote long-term sustainability.
By addressing these objectives, this study provides specific and detailed data on the
concentrations of key hazardous substances, including polycyclic aromatic hydrocarbons
(PAHs), heavy metals (HMs), and persistent organic pollutants (POPs), across different
matrices (water, sediment, and biota). This valuable dataset is integral to the upcoming
national assessment of the third cycle of MSFD reporting (2018–2023) and offers detailed
insights into contamination hotspots, distribution, and the effectiveness of current regu-
latory measures.
This study provides a comprehensive assessment of the contamination status of the
marine ecosystem, conducted within the MSFD framework from 2020 to 2022. Data on
eutrophication [2], contamination, pelagic and benthic habitats were collected from 70 sta-
tions during five oceanographic expeditions, encompassing transitional, coastal, shelf,
and offshore waters. While regular monitoring network extends up to 100 m in depth, this
study offered us the unique opportunity to evaluate open sea waters, beyond a 200 m
isobath. Our investigations focused on key contaminants, including heavy metals (HMs),
Sustainability 2024, 16, 9785 4 of 49

polycyclic aromatic hydrocarbons (PAHs), and persistent organic pollutants (POPs), such
as organochlorinated pesticides (OCPs) and polychlorinated biphenyls (PCBs), assessing
their presence in relevant matrices.
The study offers crucial insights into the present state of Black Sea contamination, a
regional sea facing increasing environmental and geopolitical challenges. The integrated
assessment reveals areas with elevated contaminant levels, largely due to riverine inputs,
urban runoff, harbor activities, and industrial discharges. Even offshore waters, which are
typically less impacted, showed measurable pollutant levels, indicating the pervasive na-
ture of contamination in the region.
This study plays a pivotal role in advancing efforts to achieve GES under the MSFD
by offering valuable insights into Black Sea contamination patterns. The findings under-
score the need for enhanced regulatory measures, improved waste management practices,
and the stricter enforcement of pollution control regulations. This study highlights the
necessity of sustained monitoring and collaborative regional efforts.

2. Materials and Methods


2.1. Research Area
The research was conducted in the northwestern Black Sea, within Romania’s exclu-
sive economic zone, a region characterized by unique environmental pressures and geo-
graphical features that significantly influence pollution dynamics. Five oceanographic ex-
peditions were carried out between June 2020 and September 2022 aboard RVs “Steaua de
mare” and “Mare Nigrum”. The sampling campaigns were conducted during the warm
seasons, in line with typical monitoring schedules and operational considerations. A com-
prehensive station network across all MSFD reporting regions was covered, resulting in
the collection of 145 surface water samples and 116 sediment samples for contaminant
analysis. The sediment sampling stations coincided with those of the water samples (Fig-
ure 1a), with the exception of stations deeper than 500 m. Additionally, 18 mollusk sam-
ples (Mytilus galloprovincialis, Rapana venosa) were collected from coastal and shelf areas
during 2020–2022 (Figure 1b).

(a)
Sustainability 2024, 16, 9785 5 of 49

(b)
Figure 1. (a) Locations of water and sediment sampling stations, 2020–2022. (b) Map of mollusk
sampling stations, 2020–2022.

The study region was subdivided into four designated marine reporting units
(MRUs) (Figure 2):
Transitional waters (BLK_RO_RG_TT03): From the baseline to the 29 m isobath.
Coastal waters (BLK_RO_RG_CT): From the baseline to the 29 m isobath.
Shelf waters (BLK_RO_RG_MT01): From the 30 m isobath to the 200 m isobath.
Offshore waters (BLK_RO_RG_MT02): Beyond the 200 m isobath.
The Romanian Black Sea sector (244 km coastline, comprising 6% of the Black Sea’s
total) faces significant environmental pressures due to a confluence of factors. The area is
influenced by the Danube River’s discharge in the north and industrialized urban centers
in the south, while a surge in summer tourism further complicates matters. Other major
rivers, like the Dniester, Dnieper, Don, and Bug, also have a substantial impact on the
northwestern region. The southern coast is defined by major activities including
wastewater treatment, beach restoration, maritime transportation, fishing, and oil and gas
extraction [4,37]. While sewage treatment plants have faced challenges, improvements
were noted in 2018 due to upgrades and expansions [2]. The major ports of Constanta,
Mangalia, and Midia are crucial for maritime transport. Offshore oil and gas exploration
and production have been significant since the 1970s, contributing 8% of Romania’s oil
and gas output [4]. Environmental pressures primarily stem from shipping, coastal de-
fense, and construction activities [7]. Shipping is the most significant contributor, causing
pollution and marine litter. Coastal defense and flood protection measures disrupt natural
sediment dynamics, while dredging and offshore construction lead to habitat loss and
biodiversity changes [2,4,7].
The geographical region offers valuable insights into the broader pollution dynamics
of the Black Sea due to its varied environmental pressures. The interplay of riverine inputs
and intense industrial and maritime activities along the coast make this sector particularly
significant for studying pollutant distribution patterns [38]. The mix of pollutants from
urban, agricultural, and industrial sources, including contaminants such as heavy metals,
organic compounds, and nutrients, combined with seasonal tourism, contributes to a com-
plex contamination landscape [4]. This area’s semi-enclosed nature further exacerbates
pollutant retention and distribution, making it an ideal site for understanding how con-
taminants behave in both coastal and offshore environments. Eutrophication, a process
driven by excessive nutrient inputs that can lead to harmful algal blooms and oxygen de-
pletion, is also a significant concern in this region due to agricultural runoff and urban
Sustainability 2024, 16, 9785 6 of 49

wastewater discharges [2,39]. The regional characteristics provide a microcosm for as-
sessing pollution dynamics across the wider Black Sea ecosystem.

Figure 2. The four designated marine reporting units (MRUs).

2.2. Sample Collection and Initial Preparation Methods


Water Sampling: Surface water samples were collected using Niskin bottles, which
are specifically designed to prevent contamination during collection. All samples were
taken from the uppermost layer (0–1 m) across various locations, ensuring consistency in
the sampling depth. This method ensures that the data reflect the surface water layer’s
quality, which is most affected by atmospheric interactions, runoff, and human activities.
Immediately after collection, the samples were stored at 4–8 °C to preserve their integrity
for further analysis [40].
Sediment Sampling: Surface sediments were collected using a Van Veen grab sam-
pler, which is ideal for retrieving undisturbed sediment samples from the top 2–5 cm
layer, which represents recent pollutant deposition [41]. The design of the grab minimizes
disturbance to the sediment profile, ensuring that the surface layer remains intact, and
that the data accurately reflect current contamination levels. After collection, the samples
were stored at −20 °C.
Mollusk Sampling: Mollusks (Mytilus galloprovincialis and Rapana venosa) were col-
lected using a biological dredge. The dredge method ensures that multiple individuals are
gathered from each sampling location, allowing for composite samples (5–10 individuals)
that are representative of the area [42]. The mollusks were harvested from both coastal
and shelf waters, providing a comprehensive view of contaminant levels across different
habitats. Following collection, the mollusks were promptly stored in freezer boxes to
maintain sample integrity before further laboratory analysis.
Sustainability 2024, 16, 9785 7 of 49

Sampling efforts focused on surface water, surface sediment, and mollusks, with no
depth-specific adjustments required for water or sediment. The sampling strategy consid-
ered transitional, coastal, shelf and offshore areas, to capture spatial variations in contam-
ination levels. Consistent methods were used across locations to ensure the comparability
of results.
In the laboratory, sediments and mollusks (whole soft tissue) were subjected to ly-
ophilization, resulting in the complete removal of water content. The freeze-dried samples
were subsequently analyzed for inorganic and organic pollutants. The sediments were
sieved to eliminate coarse fragments larger than 0.5 mm. The dried samples were homog-
enized using an electric grinder [40–42].

2.3. Analytical Techniques


2.3.1. Heavy metals ( HMs)
The concentrations of copper (Cu), cadmium (Cd), lead (Pb), nickel (Ni), and chro-
mium (Cr) in seawater were measured from unfiltered, acidified water samples (acidified
to pH 2 using ultrapure HNO3). For the analysis of heavy metals (HMs) in sediment and
biological tissues, approximately 0.05–0.5 g of dried material was digested with 10 mL of
concentrated HNO3 inside sealed Teflon vessels on a hot plate at 120 °C. The resulting
solution was diluted to 100 mL with deionized water (18.2 MΩ·cm, Millipore, Burlington,
MA, USA). The HMs concentrations were determined using a High-Resolution Contin-
uum Source Atomic Absorption Spectrometer (HR-CS ContrAA 800 G, Analytik Jena,
Jena, Germany). Calibration standards were prepared from Merck stock solutions for each
element with the following concentration ranges: 0–50 µg/L for Cu and Ni, 0–10 µg/L for
Cd, 0–25 µg/L for Pb, and 0–50 µg/L for Cr. Each sample was tested in triplicate, and the
average value was recorded. The detection limits for the HMs varied between 0.001 and
0.01 µg/L, depending on the element. Standardized protocols were employed throughout
the analytical procedures to ensure accuracy and consistency [40,41,43]. The HMs concen-
trations in seawater are reported in µg/L, while in sediments they are expressed as µg/g
dry weight (dw), and in biological tissues as µg/g tissue dry weight (dw).

2.3.2. Persistent Organic Pollutants (POPs’): Organochlorinated Pesticides (OCPs) and


Polychlorinated Biphenyls (PCBs), and Polycyclic Aromatic Hydrocarbons (PAHs)’ Ex-
traction in Biota
For the analysis of POPs, approximately 2 g of biota sample was extracted using a
microwave-assisted method with an acetone/hexane (1:1) mixture. The internal standard,
2,4,5-Trichlorobiphenyl, was added to the samples to assess the recovery efficiency
throughout the analytical process. Lipids were removed by adding 10 mL of concentrated
H2SO4, followed by cleanup with copper and fractionation using a florisil column. The
samples were then concentrated under a nitrogen stream in a water bath and analyzed
using GC-ECD [44].
PAH compounds were extracted from approximately 2 g of freeze-dried tissues using
the Soxhlet extraction method. The internal standard, 9,10-dihydroanthracene, was added
to assess the recovery efficiency of the analytical procedure. Samples were extracted for 8
h with 250 mL of methanol using the Soxhlet apparatus. The resulting extracts were sa-
ponified by adding 20 mL of 0.7 M KOH and 30 mL of water, followed by reflux for 2 h.
The PAH-containing fraction was then concentrated under a gentle nitrogen stream to a
final volume of 1 mL and analyzed by GC-MS. [44].

2.3.3. POPs’ and PAHs’ Extraction in Seawater and Sediments


Seawater samples were extracted using a hexane/dichloromethane (3:1) mixture in a
funnel, while sediment samples underwent microwave extraction. Following extraction,
cleanup was performed with copper, and fractionation was conducted using a florisil col-
umn for OCPs and an alumina/silica column for PAHs. The samples were then
Sustainability 2024, 16, 9785 8 of 49

concentrated under a nitrogen stream in a water bath and analyzed by GC-ECD for OCPs
and GC-MS for PAHs. Internal standards, namely 2,4,5-Trichlorobiphenyl for POPs and
9,10-dihydroanthracene for PAHs, were added to assess the recovery efficiency of the an-
alytical procedures [44].

2.3.4. Gas Chromatographic Analyses of POPs and PAHs


For the analysis of OCPs and PCBs, concentrated extracts were examined using a
Perkin Elmer Clarus 500 gas chromatograph equipped with an electron capture detector
(GC/ECD) (PerkinElmer Inc., Waltham, Massachusetts, USA). The quantification of spe-
cific OCPs and PCBs was performed by comparing the peak areas of the samples to those
of known standards. Calibration curves for GC-ECD were generated using individual
standards for nine OCPs (Hexachlorobenzene, Lindane, Heptachlor, Aldrin, Dieldrin, En-
drin, p,p’DDE, p,p’DDD, and p,p’DDT) and 7 PCBs (PCB 28, PCB 52, PCB 101, PCB 118,
PCB 138, PCB 152, and PCB 180), with concentrations ranging between 1000 and 5000
µg/mL dissolved in methanol.
For PAH analysis, the concentrated extract was examined using a Perkin Elmer Cla-
rus 690 system with gas chromatography–mass spectrometry (GC/MS) (PerkinElmer Inc.,
Waltham, Massachusetts, USA). A standard mixture containing the 16 priority PAHs—
naphthalene (Na), acenaphthylene (Ac), acenaphthene (Ace), fluorene (Flu), anthracene
(An), phenanthrene (Ph), fluoranthene (Fln), pyrene (Pyr), benzo[a]anthracene (BaA),
chrysene (Chr), benzo[a]pyrene (BaP), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene
(BkF), benzo[g,h,i]perylene (BghiP), indeno [1,2,3-cd]pyrene (IP), and dibenzo[a,h]anthra-
cene (DaA)—dissolved in toluene at individual concentrations of 100 µg/mL was used to
calibrate the GC-MS [44].
The data were interpreted using MS Excel 365, Statistica (TIBCO Software Version
14.0.1.25) [45], Ocean Data View (ODV) version 5.1.7 [46] and ArcGIS Desktop 10.7 soft-
ware [47]. Distribution maps were created using IDW interpolation in ArcGIS.

2.4. Methodology for Contamination Status Assessment


Good Environmental Status (GES) has been defined based on Criterion D8C1 (De-
scriptor 8) and Criterion D9C1 (Descriptor 9). For these criteria, GES, associated indica-
tors, and environmental objectives have been defined (Table 1).
The marine assessment areas , identified as reported to the European Environment
Agency (EEA), WISE-MARINE (https://sdi.eea.europa.eu/catalogue/srv/eng/cata-
log.search#/metadata/a14375b6-13fa-44d2-9e01-f8bee5954dbb , accessed on 29 September
2024), are designated with the following codes: transitional waters—BLK_RO_RG_TT03,
coastal waters—BLK_RO_RG_CT, marine shelf area—BLK_RO_RG_MT01 and offshore
waters—BLK_RO_RG_MT02 (Descriptor 8), respectively (Descriptor 9).
The evaluation of Descriptor 8 focused on the contaminant concentrations in water
and sediment samples collected between 2020 and 2022. Data were centralized, processed,
statistically analyzed, and compared to the proposed threshold values for GES [48]. The
definition of GES for Descriptor 8 involved, starting with the previous assessment in the
framework of MSFD reporting, a comprehensive review of existing methodologies at the
national, regional, and European levels [29]. An appropriate methodology was selected
for the analyzed group of contaminants, and background values and threshold values
were carefully assessed [49].
For sediments, given the absence of European legislation specifying contaminant
threshold values, we selected established benchmarks, such as Effect Range Low levels
(ERL) [50,51], which are widely used to assess sediment quality and the potential ecolog-
ical risks associated with contaminant levels in marine and freshwater environments
[49,51–53]. The Effect Range Low (ERL), developed by Long and Morgan (1991) under the
US Environmental Protection Agency (US EPA) [50], is a sediment quality guideline used
to evaluate the potential ecological effects of contaminant concentrations in sediments. It
Sustainability 2024, 16, 9785 9 of 49

represents the lower threshold within a range of contaminant concentrations where ad-
verse biological effects are rarely observed.
ERL indicates a concentration below which adverse effects on marine life are unlikely
to occur, making it a conservative benchmark to protect ecosystems [53]. Effect Range Me-
dian (ERM), often used alongside ERL, represents a higher threshold where adverse ef-
fects are more frequently observed [51]. ERL values are derived from long-term data, link-
ing contaminant concentrations to the observed biological effects [50]. They provide an
important tool for sediment quality assessment, allowing researchers to interpret whether
the measured concentrations of specific contaminants (e.g., heavy metals, organic pollu-
tants) are likely to pose ecological risks.
In this study, ERL values were used to determine appropriate threshold concentra-
tions for contaminants in sediments, especially in the absence of specific European legis-
lation. When the contaminant concentrations in sediments exceed ERL values, they may
indicate a potential risk to benthic organisms, but values below ERL values generally sug-
gest that the sediment is safe for marine life [51,53]. ERL values provide a scientifically
validated foundation for determining threshold values in sediment contamination assess-
ments. By applying these widely recognized thresholds [52], we ensure that the risk of
harmful effects on marine ecosystems is minimized. For contaminants without specific
European or national standards, ERL values serve as an effective and precautionary guide-
line for assessing sediment quality and maintaining compliance with the goals of the
MSFD [49].
This study aligns with European environmental regulations, specifically Directive
2013/39/EU (Priority Substances Directive), which establishes Environmental Quality
Standards (EQS) for priority substances in surface waters [36]. Directive 2013/39/EU is an
important amendment to the Water Framework Directive (WFD, Directive 2000/60/EC)
[33]. The WFD was adopted by the European Union in 2000, and its primary goal is to
establish a comprehensive framework for the protection and sustainable management of
inland surface waters, transitional waters, coastal waters, and groundwater across EU
member states. It requires that all European waters achieve “good status” by setting eco-
logical and chemical standards for water bodies, targeting pollution reduction, and pro-
moting sustainable water use [33]. Directive 2013/39/EU focuses on setting specific Envi-
ronmental Quality Standards (EQSs) for priority substances in surface waters, addressing
pollutants that pose significant risks to aquatic environments and human health. By es-
tablishing and updating the threshold limits for pollutants such as heavy metals and or-
ganic compounds [36], it plays a crucial role in harmonizing water quality goals across the
WFD and MSFD. It aims to reduce harmful substances in both freshwater and marine
environments, aiding in the achievement of Good Ecological Status under the WFD [33]
and Good Environmental Status under the MSFD [22].
Most pollutants evaluated in this research are among the substances regulated under
this directive: cadmium, lead, nickel, anthracene, naphthalene, fluoranthene, benzo(a)py-
rene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(g,h,i)perylene, HCB, lindane,
heptachlor, the sum of cyclodiene pesticides, p,p’ DDT, and total DDT. By comparing the
measured concentrations to the Maximum Allowable Concentration (MAC-EQS) values
set by the directive, we aim to assess the potential ecological risks posed by short-term
contamination events in the seawater. This approach ensures that our findings are directly
relevant to European regulatory frameworks and can inform effective environmental
management strategies [22,36].
Descriptor 9 assessed the levels of contaminants in edible seafood. The criterion used,
D9C1, evaluated whether these levels exceeded the established Maximum Admissible
Concentration (MAC) for organisms caught in the wild. Data available between 2020 and
2022 on the contaminant concentrations in commercially important mollusk species (Myti-
lus galloprovincialis and Rapana venosa), harvested from coastal waters and the shelf zone,
were analyzed and compared to target values for GES. The definition of GES was based
on the MACs imposed by the current European or national legislation for the following
Sustainability 2024, 16, 9785 10 of 49

substances: Cd, Pb, Sum of PCB28, PCB52, PCB101, PCB138, PCB153 and PCB180 (total
ICES-6), OCPs (HCB, lindan, aldrin, endrin, dieldrin, p,p’DDE, p,p’ DDD,p,p’ DDT),
Benzo(a)Pyrene, and the sum of PAHs (Benzo(a)Pyrene, (Benzo(a)anthracene,
Benzo(b)floranthene and Chrysene) [34,54].
To determine if the marine environment has a Good Environmental Status (GES), the
methodology requires that 75% of the concentrations for an individual compound meas-
ured over the evaluation period in each matrix are below threshold values [22,29,31]. The
following formula illustrates how the exceedance rate is calculated for GES determination:

Exceedance Rate % = × 100

where Nexceedances is the number of samples exceeding the EQS, and Ntotal is the total number
of samples analyzed. Exceedance rates provide insight into the frequency and scale of
contaminant breaches, highlighting areas of potential environmental concern. A maxi-
mum exceedance rate of 25% is accepted to ensure that most of the marine environment
is not contaminated beyond acceptable levels.
Using the 75th percentile allows for some natural variation in pollutant concentra-
tions while still ensuring that most of the environment is protected. It provides a safety
margin to account for factors like seasonal variations, localized pollution events, or ana-
lytical uncertainties. Achieving GES for a specific pollutant does not imply zero contami-
nation. It indicates that the overall ecosystem is in good condition, but it does not mean
that there are no contaminants present, since a maximum of 25% of EQSs surpassing val-
ues are considered acceptable. Even small exceedances can have impacts, considering that
the effects of contaminants can be cumulative, and even low levels over time can have
adverse effects on the ecosystem [55].
Following the evaluation for each individual compound, the “One Out, All Out”
(OOAO) approach was further used in contamination assessment. The One Out, All Out
(OOAO) method is a precautionary approach used in environmental assessments under
frameworks like the WFD and MSFD [33,56]. This method dictates that if any single ele-
ment or contaminant within an assessment area (such as a marine reporting unit) fails to
meet its threshold or target level, the entire area is classified as failing to achieve Good
Environmental Status (GES). OOAO is designed to ensure stringent environmental pro-
tection by identifying even minor exceedances that could signal potential ecological risks.
However, while effective in highlighting problem areas, OOAO is sometimes critiqued for
its conservative nature, as it may not account for the overall ecological health if only one
component is slightly out of compliance [56,57]
Our methodology for contamination status assessment essentially states that if one
or more substances within a specific group is non-GES, the entire group is considered not
achieving GES. The OOAO principle is applied sequentially, starting from individual pol-
lutants, groups of compounds and matrices, and progressing to marine reporting units
(MRUs). In other words, if the 75th percentile of contaminant concentrations exceeds the
threshold value at any level, the component (compound, group, or matrix) and potentially
the entire marine reporting unit is considered contaminated (non-GES) [29].
Sustainability 2024, 16, 9785 11 of 49

Table 1. Summary of criteria, indicators, and thresholds used for national GES evaluation—De-
scriptors 8 and 9.

Threshold
Criteria Indicators GES Definition
Values
D8C1:
In coastal and territorial waters, contami- Concentrations of the
nant concentrations must adhere to the relevant contaminants
following thresholds: detected in suitable ma-
(a) For contaminants listed in point 1(a) trices (water, sediment)
The threshold
of the criteria elements, the levels speci- are either below levels
values selected
fied by Directive 2000/60/EC; that could cause nega-
in accordance
(b) If contaminants from point (a) are de- tive effects or show a
HMs, POPs, PAHs with Directive
tected in a matrix without an established declining trend [22]
concentrations in 2000/60/EC
value under the Directive, Member States
seawater (surface), and sediments (EQS) [33,36] or
will set the concentration through re- The 75th percentile of
[29]. based on the na-
gional or sub-regional cooperation; contaminants concen-
tional or re-
(c) For additional contaminants noted in trations per Marine Re-
gional values
point 1(b), Member States will determine porting Unit (MRU) and
[49,51–54]
concentration limits for specific matrices matrix should not ex-
(water, sediment, or biota) that may pose ceed the target values
pollution risks, taking into account their during the evaluation
significance within and beyond coastal period [29].
and territorial waters [31].
Cd and Pb in mollusks

Sum of PCB28, PCB52, PCB101,


D9C1: Contaminants levels in
PCB138, PCB153 and PCB180
The contaminant levels in edible tissues mollusks should be be-
(total ICES-6) in mollusks
of wild-caught seafood (including fish, low MACs set out by
crustaceans, mollusks, echinoderms, sea- European [34] and na-
OCPs
weed) must not exceed: tional legislation [58] for
(HCB, lindan, MACs from Eu-
(a) The maximum levels specified in EC human consumption.
aldrin, endrin, ropean [34] or
Regulation for listed contaminants [34],
dieldrin, p,p’ national legisla-
which serve as the threshold values for The 75th percentile of
DDE, p,p’ DDD, tion [58]
this Decision; contaminant concentra-
p,p’ DDT) in mollusks
(b) For additional contaminants not cov- tions in mollusks is be-
ered by EC Regulation, threshold values low the regulated levels
Benzo(a)Pyrene,
determined by Member States through throughout the evalua-
Sum of PAHs (Benzo(a)Pyrene,
regional or sub-regional cooperation [31]. tion period [29].
(Benzo(a)anthra-
cene,Benzo(b)floranthene and
Chrysene) in mollusks

3. Results
3.1. Descriptor 8: Contaminant Assessment
The aim of the assessment was to analyze the presence and levels of harmful contam-
inants in marine waters and sediments. By analyzing data from various locations and
comparing it to established thresholds, the study assessed the environmental status of
each marine reporting unit (MRU) based on the contaminant concentration levels. The
specific contaminants of interest were HMs, POPs (OCPs and PCBs), and PAHs. For each
individual compound within these categories, data were analyzed to compare the meas-
ured concentrations with the established threshold values that define good ecological
Sustainability 2024, 16, 9785 12 of 49

status. The results were presented for each pollutant category, marine reporting unit, and
matrix (water and sediment). A key statistical parameter used in the assessment was the
75th percentile, which represents the value below which 75% of the data fall. This param-
eter served as a benchmark to evaluate the overall level of contamination in each region
and matrix (GES, non-GES).

3.1.1. Transitional Waters—BLK-RO-RG-TT03


The data presented in Table 2 are based on 20 seawater and 19 sediments samples
collected between 2020 and 2022. The 75th percentile was calculated by sorting the data
and selecting the value below which 75% of the results fall, ensuring that natural variabil-
ity is accounted for. GES is achieved when the 75th percentile is below the EQS, meaning
that exceedance rates are less than 25%. The percentage of samples exceeding threshold
values (EQS or ERL) was calculated to assess the frequency of contamination above ac-
ceptable levels, providing insight into potential environmental risks.

Persistent Organic Pollutants (POPs)


Waters receiving significant freshwater input from the Danube River were found to
be contaminated with persistent organic pollutants. In 14% to 72% of the water samples
analyzed, the levels of these pollutants exceeded safe limits for a healthy ecosystem (Fig-
ure 3). However, hexachlorobenzene and heptachlor were exceptions, meeting the stand-
ards for GES. In sediments, most pollutants remained within safe limits, except for lin-
dane, resulting in a poor overall environmental status (non-GES) for both the water and
sediment regarding POPs. This is due to the application of the “one out, all out” (OOAO)
approach, meaning that if even one compound exceeds safe limits, the entire MRU is clas-
sified as being in poor condition (Table 2).
It is important to mention that the heptachlor detection limit (LOD 0.003 ug/L) ex-
ceeds the regulatory threshold for seawater [36], which introduces some uncertainty. This
discrepancy arises from the technical limitations of the analytical method, where the LOD
surpasses the threshold value. Although the detectable concentrations comply with GES
criteria (75% of values being close to LOD) in some cases, concentrations below the LOD
remain indeterminate. This is a common challenge in environmental assessments, espe-
cially for this compound [59].

Figure 3. Exceedances of the threshold values for OCPs in the transitional waters, 2020–2022.

Polycyclic Aromatic Hydrocarbons (PAHs)


The levels of PAHs in the Danube-impacted waters were found to be low. Only a very
small number of samples showed PAH concentrations that exceeded the safe limits for a
healthy ecosystem (9% for anthracene and 1% for benzo(k)fluoranthene and
Sustainability 2024, 16, 9785 13 of 49

benzo(g,h,i)perilen). As a result, both the water and sediment samples were regarded as
being in good environmental condition regarding PAHs (Table 2).

Heavy Metals (HMs)


The HMs levels in transitional waters were generally below the EQS, indicating good
ecological status. Copper (4%) and lead (8%) had some exceedances, but the percentages
were relatively low. This suggests that while there is some metal contamination in the
water, it is not at levels that significantly threaten the ecosystem. The situation was more
concerning for sediment. Nickel significantly exceeded the EQS in many samples (67%),
leading to a non-GES status. Copper and lead also had exceedances, but to a lesser extent
(copper 24% and lead 17%) (Table 2).
Previous studies reported that nickel (Ni) concentrations in the north-western Black
Sea sediments ranged from 1 to 207 µg/g, with an average of 66.4 µg/g [60–62]. In some
areas, these concentrations exceeded the Effect Range Low (ERL) value [61]. Studies indi-
cate that Ni shows a strong geochemical association with Fe2O3, reflecting its natural
origin from regional lithology [60,61]. Furthermore, its correlation with total organic car-
bon (TOC) suggests the influence of terrigenous material and biogenic sources, where or-
ganic matter can adsorb and concentrate metals [61–63]. While these elevated Ni levels
surpass Environmental Quality Standards (EQSs), they are consistent with the naturally
high background levels of the Black Sea, as demonstrated through normalization using
elements such as Rb or Fe [60,61]. Consequently, while Ni concentrations exceed regula-
tory thresholds, this primarily reflects natural geochemical inputs rather than anthropo-
genic contamination [61–63]. Further studies are recommended to better differentiate be-
tween natural and anthropogenic sources of heavy metals in sediments [64–67].
The integration of the results for each compound within contaminant groups, using
OOAO, highlighted both a poor ecological status (non-GES) for some contaminant
groups/matrices and a good ecological status (GES) for other contaminant groups/matri-
ces.
Through the integration of all the results together, with all contaminant groups
(HMs, POPs, PAHs) and matrices, the overall ecological status of the transitional waters
MRU-BLK-RO-RG-TT03 was found to be poor (non-GES), based on the OOAO principle
(Table 3). The OOAO principle means that if even one contaminant group within a specific
matrix (like water or sediment) is found to have a poor status, then the overall ecological
status is considered non-GES. In other words, if any part of the system is unhealthy, the
whole is considered unhealthy. Overall, the conclusion is that despite some individual
contaminant groups having good ecological status, the overall health of the transitional
water area is poor due to the presence of at least one contaminant group with a non-GES
status.

Table 2. Status of the transitional waters, 2020–2022 (POPs, PAHs, HMs).

Environmental Status per


Matrix Compound 75th Percentile Threshold Value
Compound
HCB 0.018 0.05 GES
Lindane 1.603 0.02 Non-GES
Heptaclor * 0.003 0.00003 GES
Sum of cyclodiene pesticides 3.623 0.005
Water p,p’DDT 2.000 0.01 Non-GES
(µg/L) DDT total 6.751 0.025
Naphthalene 0.0201 130
Anthracene 0.0001 0.1
GES
Fluoranthene 0.0001 0.12
Benzo(a)pyrene 0.0001 0.027
Sustainability 2024, 16, 9785 14 of 49

Environmental Status per


Matrix Compound 75th Percentile Threshold Value
Compound
Benzo(b)fluoranthene 0.0001 0.017
Benzo(k)fluoranthene 0.0001 0.017
Benzo(g,h,i)perylene 0.0001 0.00082
Copper 14.08 30
Cadmium 0.32 1.5
Lead 2.03 14 GES
Nickel 4.30 34
Chromium 5.85 100
HCB 1.0981 20 GES
Lindane 3.2295 3 Non-GES
Dieldrin 0.0178 2
p,p’DDE 0.0020 2.2
PCB 28 0.0212 1.7
PCB 52 0.0348 2.7
PCB 101 0.0060 3 GES
PCB 118 0.0040 0.6
PCB 153 0.0090 40
PCB 138 0.0070 7.9
PCB 180 0.0030 12
Sediment Naphthalene 10.15 160
Acenaphthene 0.1 16
(POPs and PAHs Phenanthrene 17.77 240
µg/kg dry weight; Anthracene 0.1 85
HMs µg/g dry Fluoranthene 27.57 600
weight) Pyrene 30 665
GES
Benzo[a] anthracene 9.939 261
Chrysene 9.322 384
Benzo[a]pyrene 29.10 430
Benzo(g,h,i)perylene 0.1 85
Indeno(1,2,3-c,d)pyrene 0.1 240
Total ∑HAP 158.644 1000
Copper 40.70 40
Cadmium 0.41 1.2 GES
Lead 45.59 47
Nickel 57.99 35 Non-GES
Chromium 51.46 81 GES
* The limit of detection (LOD) for heptachlor is higher than the threshold value stipulated by Di-
rective 39/2013. The percentile refers to the exceedances of LOD.

GES achieved GES not achieved

Table 3. Overall assessment of environmental status in the transitional waters, 2020–2022.


Environmental Status per Environmental Status
MRU Matrix Group of Compounds
Group of Contaminants for the Assessment Area
POPs Non-GES
Transitional waters Water PAHs GES
Non-GES
BLK-RO-RG-TT03 HM GES
Sediment POPs Non-GES
Sustainability 2024, 16, 9785 15 of 49

Environmental Status per Environmental Status


MRU Matrix Group of Compounds
Group of Contaminants for the Assessment Area
PAHs GES
HMs Non-GES

GES achieved GES not achieved

3.1.2. Coastal Waters—BLK-RO-RG-CT


The data presented in Table 4 are based on 37 seawater and 33 sediments samples
collected between 2020 and 2022. The 75th percentile was calculated by sorting the data
and selecting the value below which 75% of the results fall, ensuring that natural variabil-
ity is accounted for. GES is achieved when the 75th percentile is below the EQSs, meaning
that exceedance rates are less than 25%. The percentage of samples exceeding threshold
values (EQS or ERL) was calculated to assess the frequency of contamination above ac-
ceptable levels, providing insight into potential environmental risks.

Persistent Organic Pollutants (POPs)


In 11–89% of samples, most POP concentrations in coastal waters exceeded the GES
thresholds (Figure 4). Hexachlorobenzene (HCB) and heptachlor were the only com-
pounds that met the criteria for GES. Consequently, the water quality assessment resulted
in a non-GES status (Table 4).
In sediments, all compounds were within the range for GES, and this matrix was
therefore classified as having a good status.

Figure 4. Exceedances of the threshold values for OCPs in coastal waters, 2020–2022.

Table 4. Status of the coastal waters, 2020–2022 (POPs, PAHs, HMs).

Environmental Status per


Matrix Compound Percentile 75th Threshold Value
Compound
HCB 0.004 0.05 GES
Lindane 1.749 0.02 Non-GES
Heptaclor * 0.003 0.00003 GES
Water Sum of cyclodiene pesticides 1.992 0.005
(µg/L) p,p’DDT 1.507 0.01 Non-GES
DDT total 7.143 0.025
Naphthalene 0.022 130
GES
Anthracene 0.0001 0.1
Sustainability 2024, 16, 9785 16 of 49

Environmental Status per


Matrix Compound Percentile 75th Threshold Value
Compound
Fluoranthene 0.0001 0.12
Benzo(a)pyrene 0.0001 0.027
Benzo(b)fluoranthene 0.0001 0.017
Benzo(k)fluoranthene 0.0001 0.017
Benzo(g,h,i)perylene 0.0001 0.00082
Copper 11.05 30
Cadmium 0.08 1.5
Lead 1.74 14 GES
Nickel 2.34 34
Chromium 4.71 100
HCB 0.8819 20
Lindane 2.1794 3
Dieldrin 0.0034 2
p,p’DDE 0.0020 2.2
PCB 28 0.0115 1.7
PCB 52 0.0266 2.7 GES
PCB 101 0.0060 3
PCB 118 0.0040 0.6
PCB 153 0.0090 40
PCB 138 0.0070 7.9
PCB 180 0.0030 12
Sediment Naphthalene 1.4577 160
Acenaphthene 0.1 16
(POPs and PAHs Phenanthrene 16.4169 240
µg/kg dry weight; Anthracene 0.1 85
HMs µg/g dry Fluoranthene 14.5104 600
weight) Pyrene 13.6701 665
GES
Benzo[a] anthracene 8.2683 261
Chrysene 7.0990 384
Benzo[a]pyrene 24.5123 430
Benzo(g,h,i)perylene 0.1 85
Indeno(1,2,3-c,d)pyrene 3.0244 240
Total ∑HAP 126.313 1000
Copper 17.01 40
Cadmium 0.22 1.2
Lead 14.10 47 GES
Nickel 30.02 35
Chromium 34.10 81
* The limit of detection (LoD) for heptachlor is higher than the threshold value stipulated by Di-
rective 39/2013. The percentile refers to the exceedances of LoD.

GES achieved GES not achieved

Polycyclic Aromatic Hydrocarbons (PAHs)


These compounds were found to be at rather low levels in the coastal waters. None
of the samples exceeded the threshold values, except benzo(g,h,i)perilen (4%). Both the
water and the sediment samples were determined to have good ecological status, based
on the 75th percentile values of the monitoring data (Table 4). This means that the overall
Sustainability 2024, 16, 9785 17 of 49

environmental condition of the coastal area, as assessed by PAHs, was considered good
(GES).

Heavy Metals (HMs)


The 75th percentile concentrations for all HMs in both the water and sediment matri-
ces were below the Environmental Quality Standards (EQSs), which means that GES is
achieved, but there are still some instances of exceedances observed. In water, only copper
(Cu) showed exceedances in 3% of samples; meanwhile, in sediment, exceedances were
observed for copper (Cu) and lead (Pb) in 3%, and nickel (Ni) in 21% of samples (Table 4).
Despite these exceedances, which were maintained below 25% (GES threshold), the eco-
logical status for all metals in the coastal area is still classified as good (GES). This indicates
that while most samples are within safe limits, isolated instances of elevated HM concen-
trations do occur.
By combining the results for elements within the contaminant group, using the
OOAO principle, both a poor and good ecological status were identified for various con-
taminant groups or matrices. While some individual pollutant groups exhibited good eco-
logical status, the presence of contaminants in other groups led to a negative overall as-
sessment. Through the integration of results obtained for all contaminant groups and ma-
trices, using the one-out-all-out (OOAO) principle, an overall poor ecological status (non-
GES) was determined for the evaluated coastal area (Table 5). This conclusion is reached
by applying the one-out-all-out principle, which states that if one component of a system
fails, the entire system is considered to have failed. In this case, even though some pollu-
tant groups were within acceptable limits, the presence of contaminants in others com-
promised the overall water quality.

Table 5. Assessment of the environmental status for coastal area, 2020–2022.

Environmental Status per Environmental


MRU Matrix Group of Compounds
Group of Contaminants Status for MRU
POPs Non-GES
Water PAHs
Coastal waters HMs
Non-GES
BLK-RO-RG-CT POPs GES
Sediment PAHs
HMs

GES achieved GES not achieved

3.1.3. Shelf Waters (BLK_RO_RG_MT01)


The data presented in Table 6 are based on 70 seawater and 61 sediment samples
collected between 2020 and 2022. The 75th percentile was calculated by sorting the data
and selecting the value below which 75% of the results fall, ensuring that natural variabil-
ity is accounted for. GES is achieved when the 75th percentile is below the EQS, meaning
that exceedance rates are less than 25%. The percentage of samples exceeding threshold
values (EQS or ERL) was calculated to assess the frequency of contamination above ac-
ceptable levels, providing insight into potential environmental risks.

Persistent Organic Pollutants (POPs)


The concentrations of most POPs in the marine waters of the shelf zone were high,
exceeding the threshold values in 19–91% of the samples (Figure 5). Hexachlorobenzene
(HCB) was the only compound that had a good ecological status. Consequently, the water
assessment resulted in a poor ecological status due to the application of the OOAO prin-
ciple (Table 6). In sediments, all compounds had a good ecological status (75th percentile
of data was below threshold).
Sustainability 2024, 16, 9785 18 of 49

.
Figure 5. Exceedances of the threshold values for OCPs in shelf marine waters, 2020–2022.

Polycyclic Aromatic Hydrocarbons (PAHs)


The concentration of these pollutants in the shelf marine waters was low, with the
75th percentile values being below the threshold values and resulting in GES in both water
and sediment. However, for fluoranthene, exceedances of the threshold values were ob-
served in water in 14% of the samples. Overall, in this reporting unit, GES was achieved
(Table 6).

Heavy Metals (HMs)


In water, all HMs have 75th percentile concentrations well below their respective En-
vironmental Quality Standards (EQSs). Exceedances of EQSs were minimal, with copper
(Cu) and cadmium (Cd) exceeding their EQSs in 2% of samples. The overall ecological
status for all HMs in the water matrix is classified as Good Ecological Status (GES). In
sediments, copper (Cu) is very close to its EQS, with a 75th percentile of 39.75 µg/g com-
pared to the EQS of 40 µg/g. Although 25% of the samples exceeded the EQS, it remains
within an acceptable limit, so the status for this element is classified as GES. Lead (Pb) and
chromium (Cr) have low exceedance rates (5% and 1% respectively) and maintain a GES
status. Nickel (Ni) is the most concerning, with a 75th percentile concentration of 47.11
µg/g, exceeding the EQS of 35 µg/g, and 54% of samples surpassing the EQS. This results
in a nickel being classified as non-GES in the sediment matrix (Table 6).
However, as we mentioned for the transitional area, previous studies reported that
the Ni concentrations in north-western Black Sea sediments consistently exceed the Effect
Range Low (ERL) values [61]. These elevated Ni levels are primarily driven by natural
geochemical processes, as indicated by the strong correlation with Fe2O3 and total organic
carbon (TOC), reflecting the naturally high background concentrations of the region, ra-
ther than significant anthropogenic contamination [60–63]. Additional research is needed
to better clarify the contributions of natural versus human-induced sources [64–67].

Table 6. Status of the shelf marine waters, 2020–2022 (POPs, PAHs, HMs).

Threshold Environmental Status per


Matrix Compound Percentile 75th
Value Compound
HCB 0.024 0.05 GES
Lindane 4.958 0.02
Heptaclor * 0.342 0.00003
Water Sum of cyclodiene pesticides 5.374 0.005 Non-GES
(µg/L) p,p’DDT 0.465 0.01
DDT total 6.501 0.025
Naphthalene 0.0172 130
GES
Anthracene 0.0001 0.1
Sustainability 2024, 16, 9785 19 of 49

Fluoranthene 0.0001 0.12


Benzo(a)pyrene 0.0001 0.027
Benzo(b)fluoranthene 0.0001 0.017
Benzo(k) fluoranthene 0.0001 0.017
Benzo(g,h,i)perylene 0.0001 0.00082
Copper 8.77 30
Cadmium 0.04 1.5
Lead 1.78 14 GES
Nickel 3.05 34
Chromium 23.24 100
HCB 0.3694 20
Lindane 0.5880 3
Dieldrin 0.1143 2
p,p’DDE 0.1031 2.2
PCB 28 0.0040 1.7
PCB 52 0.2153 2.7 GES
PCB 101 0.0097 3
PCB 118 0.0204 0.6
PCB 153 0.0090 40
PCB 138 0.0070 7.9
PCB 180 0.0030 12
Sediment Naphthalene 3.1109 160
Acenaphthene 0.100 16
(POPs and PAHs Phenanthrene 36.3327 240
µg/kg dry weight; Anthracene 0.100 85
HMs µg/g dry Fluoranthene 31.2204 600
weight) Pyrene 15.8545 665
GES
Benzo[a] anthracene 7.1434 261
Chrysene 4.0159 384
Benzo[a] pyrene 16.1312 430
Benzo(g,h,i) perylene 0.100 85
Indeno(1,2,3-c,d) pyrene 4.2325 240
Total ∑HAP 177.9075 1000
Copper 39.75 40
Cadmium 0.28 1.2 GES
Lead 31.25 47
Nickel 47.11 35 Non-GES
Chromium 36.78 81 GES
* The limit of detection (LoD) for heptachlor is higher than the threshold value stipulated by Di-
rective 39/2013. The percentage refers to LoD exceedances.

GES achieved GES not achieved

The integration of individual compound results within each contaminant group, fol-
lowing the OOAO principle, revealed a mix of ecological statuses: some contaminant
groups/matrices showed a poor ecological status, while others maintained a good ecolog-
ical status. When the results for all contaminant groups and matrices were combined us-
ing the OOAO principle, the overall environmental status for the shelf marine waters area
was determined to be non-GES (Table 7).
Sustainability 2024, 16, 9785 20 of 49

Table 7. Status of shelf marine waters, 2020–2022.

Environmental Status per Environmental Sta-


MRU Matrix Group of Compounds
Group of Contaminants tus for MRU
POPs Non-GES
Water PAHs
GES
Shelf marine waters HMs
Non-GES
BLK-RO-RG-MT01 POPs
GES
Sediment PAHs
HMs Non-GES
3.1.4. Offshore Waters (BLK_RO_RG_MT02)

GES achieved GES not achieved

The data presented in Table 8 are based on 18 seawater and 3 sediments samples
collected between 2020 and 2022. Only POPs and PAHs were analyzed in sediments. The
75th percentile was calculated by sorting the seawater data and selecting the value below
which 75% of the results fall, ensuring that natural variability is accounted for. GES is
achieved when the 75th percentile is below the EQS, meaning that the exceedance rates
are less than 25%. The percentage of samples exceeding threshold values (EQS or ERL)
was calculated to assess the frequency of contamination above acceptable levels, provid-
ing insight into potential environmental risks.

Persistent Organic Pollutants (POPs)


The concentrations of most POPs in offshore marine waters were high, surpassing
the threshold values in 22% to 100% of the samples (Figure 6). Heptachlor was the sole
compound that fulfilled the criteria for GES. Consequently, the water quality assessment
resulted in a non-GES status (Table 8). In sediments, all compounds were below threshold
values, resulting in a good overall environmental status for this matrix.

Figure 6. Exceedances of threshold values for OCPs in the offshore waters, 2020–2022.

Table 8. Status of the offshore waters, 2020–2022 (POPs, PAHs, HMs).

Threshold Environmental Status per


Matrix Compound Percentile 75th
Value Compound
HCB 0.206 0.05
Water Non-GES
Lindane 8.426 0.02
(µg/L)
Heptaclor * 0.003 0.00003 GES
Sustainability 2024, 16, 9785 21 of 49

Sum of cyclodiene pesticides 4.204 0.005


p,p’DDT 0.940 0.01
DDT total 7.836 0.025
PCB 118 0.0004 0.6 Non-GES
PCB 153 0.0006 40
PCB 138 0.0030 7.9
PCB 180 0.0012 12
Naphthalene 0.0169 130
Anthracene 0.0001 0.1
Fluoranthene 0.0001 0.12
Benzo(a)pyrene 0.0001 0.027 GES
Benzo(b)fluoranthene 0.0001 0.017
Benzo(k) fluoranthene 0.0001 0.017
Benzo(g,h,i)perylene 0.0001 0.00082
Copper 7.49 30
Cadmium 0.02 1.5
Lead 1.87 14 GES
Nickel 2.28 34
Chromium 37.64 100
* The limit of detection (LoD) for heptachlor is higher than the threshold value stipulated by Di-
rective 39/2013. The percentage refers to LoD exceedances.

GES achieved GES not achieved

Polycyclic Aromatic Hydrocarbons (PAHs)


The concentrations of these compounds in the offshore waters zone were low, with
the 75th percentile values being below the threshold values. Overall, in this reporting unit,
GES was achieved (Table 8).

Heavy Metals (HMs)


The 75th percentile of copper (Cu) concentrations is 7.49 µg/L, well below the Envi-
ronmental Quality Standard (EQS) of 30 µg/L. However, 7% of the samples exceeded the
EQS. Because these exceedances are below 25%, the overall ecological status for copper is
classified as good. The 75th percentile concentrations for Cd, Pb, Ni and Cr are all below
their respective EQS values, with no exceedances reported. Consequently, each of these
metals is classified as having a good status. Overall, the offshore marine waters show GES
for all elements assessed (Table 8).
By combining the results for each element within contaminant groups, using the
OOAO principle, a poor ecological status was identified for certain groups of contami-
nants and matrices, while others maintained a good ecological status. Overall, applying
the OOAO principle to the combined results for all contaminant groups and matrices led
to the offshore waters having a poor status (non-GES) (Table 9).
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Table 9. Environmental status of offshore waters, 2020–2022.

Ecological Status for Ecological Status


MRU Matrix Group of Compounds
Group of Contaminants of MRU
POPs Non-GES
Offshore marine Water PAHs GES
waters HMs GES Non-GES
BLK-RO-RG-MT02 POPs GES
Sediment
PAHs GES

GES achieved GES not achieved

3.2. Descriptor 9: Contaminant Assessment in Seafood


The assessment of contaminants in commercially important mollusk species (Rapana
venosa and Mytilus galloprovincialis) was carried out based on the analysis of data obtained
in each reporting zone (coastal and marine) for every compound that has MACs for hu-
man consumption defined by national and European legislation [34,58], as follows:
POPs—OCPs and the sum of six PCBs (PCB28, PCB52, PCB101, PCB138, PCB153 and PCB
180), PAHs—benzo(a)pyrene, and HMs—Cd and Pb. By comparing the measured concen-
trations to regulatory limits, this report assesses the ecological status of MRUs, using the
75th percentile as a benchmark to determine if the levels of these contaminants are within
acceptable ranges for human consumption and environmental health (GES).
The data presented in Table 10; Table 11 are based on 18 mollusk samples collected
between 2020 and 2022. The 75th percentile was calculated by sorting the data and select-
ing the value below which 75% of the results fall, ensuring that natural variability is ac-
counted for. GES is achieved when the 75th percentile is below the EQS, meaning that the
exceedance rates are less than 25%. The percentage of samples exceeding threshold values
(EQS or ERL) was calculated to assess the frequency of contamination above acceptable
levels, providing insight into potential environmental risks.

3.2.1. Coastal Waters—BLK-RO-RG-CT


Persistent Organic Pollutants (POPs)
The concentrations of most POPs in mollusk species (Rapana venosa and Mytilus gal-
loprovincialis) from coastal waters were high, exceeding the threshold values in 44–78% of
samples. Hexachlorobenzene (HCB) and endrin were the only compounds that achieved
GES (Table 10).

Polycyclic Aromatic Hydrocarbons (PAHs)


The concentrations of benzo(a)pyrene in mollusk species (Rapana venosa and Mytilus
galloprovincialis) from coastal waters were low, with no exceedances of the threshold value
(Table 10).
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Heavy Metals (HMs)


The concentrations of Cd and Pb in mollusk species were within acceptable limits for
achieving GES (Table 10).

Table 10. Environmental status for POPs, PAHs and HMs in mollusk species from the coastal waters,
2020–2022.

Compound MAC MAC Exceedances


Percentile 75th Environmental Status
POPs and PAHs (µg/g ww); HMs (µg/g dw) (%)
HCB 0.005 0.02 0 GES
Lindane 0.192 0.1 67
Heptaclor 1.295 0.02 78
Non-GES
Aldrin 0.129 0.02 56
Dieldrin 0.711 0.2 67
Endrin 0.0001 0.05 0 GES
DDT (sum of p,p’DDE, p,p’DDD, p,p’DDT) 5.867 0.01 78
Sum of 6 PCB (PCB 28, PCB 52, PCB 101, PCB Non-GES
0.139 0.075 44
153, PCB 138, PCB 180)
Benzo(a)pyrene 0.0001 10 0 GES
Cadmium (Cd) 1.282 5 0 GES
Lead (Pb) 0.122 7.5 0 GES

GES achieved GES not achieved

3.2.2. Marine Waters Shelf Area—BLK-RO-RG-MT01


Persistent Organic Pollutants (POPs)
The concentrations of most POPs in mollusk species (Rapana venosa and Mytilus gal-
loprovincialis) from shelf waters were high, exceeding the threshold values in 44–78% of
samples. Aldrin was the only compound that achieved GES (Table 11).
Polycyclic Aromatic Hydrocarbons (PAHs)
The concentrations of benzo(a)pyrene in mollusk species (Rapana venosa and Mytilus
galloprovincialis) from shelf waters were low, with no exceedances of the threshold value
(Table 11).
Heavy Metals (HMs)
The concentrations of Cd and Pb in the mollusk species from shelf waters were within
acceptable limits for GES (Table 11).
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Table 11. Environmental status for POPs, PAHs and HMs in mollusk species from the shelf waters,
2020–2022.

Compound MAC Exceedances Environmental Sta-


Percentile 75th MAC
POPs and PAHs (µg/g ww); HMs (µg/g dw) (%) tus
HCB 0.112 0.02 44
Lindane 0.551 0.1 56 Non-GES
Heptaclor 0.443 0.02 78
Aldrin 0.000045 0.02 0 GES
Dieldrin 0.366 0.2 44
Endrin 0.415 0.05 33
DDT (sum of p,p’DDE, p,p’DDD, p,p’DDT) 1.625 0.01 78 Non-GES
Sum of 6 PCB (PCB 28, PCB 52, PCB 101, PCB
0.368 0.075 67
153, PCB 138, PCB 180)
Benzo(a)pyrene 0.0185 10 0 GES
Cadmium (Cd) 3.131 5 0 GES
Lead (Pb) 0.540 7.5 0 GES

GES achieved GES not achieved

Combining the results obtained for each compound within pollutant groups high-
lighted the GES achieved for some groups of contaminants and the non-GES status of
others. By combining the results for all groups of contaminants according to the OOAO
principle, a poor status (non-GES) was determined for the two evaluation zones (Table
12).

Table 12. Environmental status for coastal and shelf zones, 2020–2022.

Environmental Status Environmental Status


MRU Group of Compounds
for Each Group of Compounds for the Evaluation Area
POPs Non-GES
Coastal waters
PAHs Non-GES
BLK_RO_RG_CT GES
HMs
POPs Non-GES
Shelf waters
PAHs Non-GES
BLK_RO_RG_MT01 GES
HMs

GES achieved GES not achieved

Our assessment of the contamination status (Descriptors 8 and 9) of the Romanian


Black Sea waters covering a 3 year-period showed that no Marine Reporting Unit (MRU)
achieved a good environmental status, following the OOAO approach.
The One Out, All Out (OOAO) approach is a widely used method for environmental
assessments, particularly in frameworks like the Water Framework Directive (WFD) and
Marine Strategy Framework Directive (MSFD) [68]. One of its key advantages is that it
acts as a precautionary tool, ensuring that even minor exceedances of individual contam-
inants are detected, thereby preventing potential cumulative or long-term environmental
harm [69]. OOAO simplifies decision-making by focusing on the worst-performing met-
ric, making it easy to identify areas of concern. This makes it particularly effective in main-
taining strict environmental standards and ensuring that ecosystems are protected from
any possible deterioration [70].
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However, the limitations of the OOAO approach are significant [71,72]. It is often
considered overly conservative, as it can classify an entire area as failing to achieve Good
Environmental Status (GES) based on a single contaminant exceeding its threshold, even
if other indicators show that the ecosystem is healthy. This rigid approach may lead to a
skewed representation of the actual environmental status, as it ignores the variability in
the impact of different contaminants [57]. Additionally, OOAO does not account for the
magnitude of the exceedance, as a small breach of a threshold may be treated the same as
a severe one, leading to potentially disproportionate management responses [69]. As a
result, OOAO can produce fragmented assessments that focus on individual substances
rather than the broader ecological context.
To overcome these limitations, OOAO should be combined with more integrated and
weighted approaches that provide a fuller picture of environmental health [73]. Both the
HELCOM Chemical Status Assessment Tool (CHASE) [74] and the Chemical Quality In-
dex (CQI), used in Italy MSFD assessments [75], apply the OOAO principle, but in a more
flexible, weighted manner. CHASE integrates data from various environmental matrices
(water, sediment, biota) and multiple contaminants, offering a holistic assessment of
chemical pollution by classifying regions as problem areas or non-problem areas based on
the exceedances of agreed-upon thresholds [76]. Similarly, the CQI approach applies
OOAO, but incorporates weighted hazard coefficients for different contaminants, priori-
tizing those with a greater ecological impact [75]. This weighted integration in both tools
reduces the risk of overly rigid assessments, as it allows minor exceedances to be contex-
tualized within the broader environmental picture.
In the Black Sea region, the CHASE tool was first tested within the ANEMONE pro-
ject [77]. The promising results suggest that CHASE should be considered for future as-
sessments in the region, which will enhance our understanding of the pollution status and
effects, enabling more effective measures to protect the marine environment.

4. Discussion
Following the evaluation of the contamination of the Romanian marine ecosystem,
based upon the MSFD methodology, the discussions will now address the detailed aspects
of pollution spatial distribution, focusing on identifying the dominant compounds, un-
derstanding their spatial distribution in various areas, and investigating potential sources
of contamination, such as rivers, wastewater treatment plants, maritime traffic and indus-
trial discharges.
Frequent contaminants in the Black Sea region include POPs, HMs, PAHs, and excess
nutrients [2,38,39,77,78]. PCBs and OCPs are particularly prevalent, linked to historical
pesticide use and industrial chemicals. HMs, including lead, cadmium, and mercury, are
also expected to be significant pollutants, largely attributed to industrial activities and
legacy pollution. PAHs, which are often linked to petroleum products and combustion
processes, are another category of pollutants that threaten the coastal ecosystem [26,79–
83].
Identifying the potential sources of these contaminants is crucial for understanding
their distribution along Romanian Black Sea sector and guiding future management ef-
forts. One of the primary sources of both PAHs and POPs is petroleum-related activities
[84], which have a long history in the region. Offshore oil and gas exploration and pro-
duction continues to be a significant contributor to the contamination observed in both
coastal and offshore waters [4]. Oil spills, operational discharges, and leaks during the
extraction, transport, and processing of crude oil introduce PAHs directly into the marine
environment [85]. This is further exacerbated by activities related to maritime transporta-
tion, including shipping lanes, oil tankers, and the three major Romanian ports—Con-
stanța, Mangalia, and Midia [86]. These ports handle significant amounts of petroleum
products, making them hotspots for petroleum-derived pollutants entering the marine
system.
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Another major source of PAHs is the combustion of fossil fuels, which releases these
compounds into the atmosphere, where they can be transported over long distances and
deposited into marine ecosystems [87]. Combustion processes related to maritime
transport (e.g., ship emissions), industrial activities, and vehicular traffic in urbanized
coastal areas all contribute to the PAH load [88]. Constanța, as one of the largest port cities
in the region, sees significant combustion-related emissions from the increased shipping
traffic and industrial activity, particularly in the petrochemical sector. The combustion of
petroleum products, such as diesel and fuel oil, produces a complex mixture of PAHs,
with high-molecular-weight PAHs (e.g., benzo[a]pyrene, chrysene) typically linked to py-
rolytic processes [85]. These compounds are more likely to originate from high-tempera-
ture combustion, such as that in ship engines, industrial furnaces, and vehicle exhausts.
In addition to direct discharges, both PAHs and POPs can enter the marine environ-
ment via atmospheric deposition [89]. Combustion processes release these contaminants
into the air, where they can bind to particulate matter and settle into the sea. This process
is especially significant for POPs, which are highly persistent and can travel vast distances
before being deposited in water bodies, contributing to both local and regional contami-
nation [90].
Industrial activities and urban runoff are also key contributors to the presence of pol-
lutants in the marine environment [91]. Urbanized areas along the coast could discharge
untreated or insufficiently treated wastewater into the sea, particularly during periods of
heavy rainfall. Wastewater treatment plants, while improved in recent years [4], still face
challenges related to the effective removal of all contaminants. Urban runoff contains a
variety of pollutants, including residues from petroleum products, heavy metals, and
POPs, which enter the marine environment through riverine inputs and stormwater
drainage systems [91].
POPs, including polychlorinated biphenyls (PCBs) and organochlorine pesticides
(OCPs), have been widely used in agriculture and industry, and despite bans or re-
strictions on their use, they persist in the environment due to their stability and long half-
lives [92]. Their presence is often linked to historical use as well as atmospheric transport
from distant sources [93]. POPs are also introduced into the marine ecosystem through
urban runoff, industrial discharges, and the improper disposal of hazardous waste [90].
The Danube River, as well as other major rivers such as the Dniester, Dnieper, Don,
and Bug, serves as a significant transport route for pollutants from inland regions [17].
These rivers carry industrial waste, agricultural runoff (including pesticides), and urban
pollutants directly into the Black Sea [26]. The Danube is a major source of contaminants
due to the diverse land uses along its course through Europe, including extensive indus-
trial and agricultural zones [94].
In particular, OCPs continue to impact the Black Sea due to legacy contamination
from agricultural runoff, riverine inputs, wastewater discharges, and atmospheric depo-
sition. Despite bans, residues persist in coastal and transitional waters, with rivers acting
as a major source from upstream agricultural regions. Urban runoff and wastewater near
coastal cities further contribute to this load, while atmospheric deposition enables long-
range transport, highlighting the complex interplay of pollution sources.

4.1. Persistent Organic Pollutants (POPs)


Our study showed that among POPs, organochlorine pesticides (OCPs) represent the
dominant compounds in the Romanian Black Sea sector, in both water and sediments,
despite their restricted or banned status (Figure 7). This persistence can be attributed to
their chemical stability, which allows them to resist environmental breakdown, and their
ability to bioaccumulate in the tissues of organisms, leading to biomagnification through-
out the food chain. Additionally, the global nature of marine currents facilitates the wide-
spread distribution of these pollutants, contaminating marine environments far from their
original sources. The continued presence of OCPs in marine environments has significant
ecological and human health implications. These pollutants disrupt marine ecosystems by
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affecting their reproductive success, immune function, and overall health status. For hu-
mans, the consumption of seafood contaminated with OCPs poses health risks, including
reproductive problems, developmental disorders, and cancer [95–99].

(a) (b)
Figure 7. Percentage contribution of the average content of organochlorine pesticides (OCPs) and
polychlorinated biphenyls (PCBs) in water (a) and sediments (b) from the Romanian Black Sea sec-
tor, 2020–2022.

The persistence of these contaminants is further reinforced by historical usage, which


has left a legacy of contamination in the environment, and their ability to bind to sediment
particles, creating long-term reservoirs. Additionally, these compounds can be volatilized
and transported over long distances through the atmosphere before being deposited in
marine environments [100].
Sediments in transitional and coastal stations exhibit higher concentrations of OCPs,
contrasting with the lower levels observed offshore. The data indicate that these areas ex-
perience the long-term accumulation of OCPs, likely due to the influence of local sources
such as riverine input and industrial activities (Figure 8).
Notably, high concentrations of OCPs in the offshore water of the northern sector of
the Romanian Black Sea (continental shelf) were observed. These elevated levels in water
suggest recent contamination events, potentially from atmospheric deposition or intensi-
fied maritime traffic, as the sediments from the same offshore locations show relatively
low OCPs concentrations (Figure 8). This discrepancy between water and sediment data
indicates that these contaminants have not yet accumulated in the sediment, supporting
the hypothesis of recent introduction rather than long-term persistence.
Atmospheric deposition may be a significant contributor to these high pesticide con-
centrations in the offshore waters where riverine and direct coastal inputs are less influ-
ential. The recent geopolitical situation, including increased maritime traffic due to grain
transport toward Romanian ports, has further intensified anthropogenic pressure in these
areas [101]. Additional influences such as the transportation of agricultural runoff via at-
mospheric processes cannot be ruled out. This spatial variation in OCP contamination,
with elevated water concentrations and low sediment accumulation in the offshore area,
highlights the complexity of pollutant dynamics in this region and underscores the need
for the continuous monitoring of both water and sediment to capture short-term contam-
ination events and their long-term ecological impact. Future investigations should focus
on distinguishing between atmospheric inputs and maritime traffic contributions to better
manage these pollution sources.
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Figure 8. Average content of organochlorine pesticides (OCPs) in waters (µg/L) and sediments
(µg/g) from the Romanian section of the Black Sea, 2020–2022.

The geographical dispersion of PCBs in water shows the complex mixture of com-
pounds to which Romanian transitional and coastal waters are exposed from various
sources, including rivers, cities, and industries. Specifically, in these areas, a wide variety
of PCB congeners is observed, reflecting the influence of both local and regional sources.
As shown in Figure 9, PCB concentrations are higher near river mouths and urban and
industrial areas. The occurrence of multiple prevalent PCB compounds suggests persis-
tent contamination, likely from historical uses and legacy pollution associated with these
pollutants. In the open marine waters, the PCB contamination pattern becomes simpler,
with PCB52 dominating the mixture (Figure 9). PCB52, being a lighter and smaller mole-
cule, is more easily transported via atmospheric pathways, which explains its widespread
distribution across more distant marine areas [102]. This highlights atmospheric deposi-
tion as a key mechanism influencing PCB contamination in offshore waters, especially for
lighter congeners like PCB52.
Similarly, in sediments, PCB distribution patterns are shaped by both riverine inputs
and industrial activities. Figure 10 highlights the prevalence of heavier PCB congeners,
such as PCB28 and PCB118, in transitional and coastal sediments, indicating localized
contamination likely associated with industrial and urban sources. In the northern part of
the open marine zone, higher concentrations of PCB28 and PCB118 are also observed,
while lighter congeners like PCB52 are more dominant in the southern areas (Figure 10).
This distribution suggests varying contamination pathways, with point sources such as
industrial activity and river discharge impacting the northern coastline, while atmos-
pheric transport and diffuse pollution are more prominent in the southern open marine
region.
The spatial variation in PCB contamination across the Romanian coastal and marine
waters demonstrates the combined effects of both localized and regional sources. Riverine
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inputs, atmospheric deposition, and maritime activities all contribute to this complex pol-
lution pattern. Future monitoring efforts should focus on distinguishing these sources
more clearly to inform targeted management strategies.

Figure 9. Percentage contribution of individual compounds to the average content of polychlorin-


ated biphenyls (PCBs) in water, 2020–2022.
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Figure 10. Percentage contribution of individual compounds to the average content of polychlorin-
ated biphenyls (PCBs) in sediments, 2020–2022.

4.2. Polycyclic Aromatic Hydrocarbons (PAHs)


PAHs showed heterogeneous values, highlighting the contribution of river input and
anthropogenic sources, particularly in the Constanța Port area (Figure 11). Constanța, as
a major hub for maritime transport and industrial activities [86], experiences significant
PAH inputs from shipping traffic, which has recently seen a substantial increase due to
the ongoing regional conflict and disruptions in traditional shipping routes. This surge in
maritime traffic, particularly with vessels rerouted to Romanian ports, has intensified
emissions from fuel combustion and cargo handling, further contributing to the PAH load
in the area. Petroleum-related activities, including oil refineries, the shipping of petroleum
products, and bunkering operations, remain major contributors to PAH emissions. These
activities release various PAHs, such as pyrene, fluoranthene, and benzo(a)pyrene, which
are common indicators of the combustion processes associated with fossil fuels.
In addition to the main port, the two satellite ports of Constanța—Midia, located 25
km to the north, and Mangalia, 38 km to the south—also play significant roles in the re-
gion’s maritime industry [86]. Midia specializes in oil and gas operations, further intensi-
fying the local PAH load, while Mangalia, a shipyard and commercial port, adds to the
pollution through shipbuilding and repair activities. Both satellite ports, together with
Constanța, contribute to the release of petroleum-derived PAHs into the marine environ-
ment. Petroleum terminals, routine discharges, accidental spills, and the handling of large
quantities of petroleum products across these ports contribute substantially to PAH con-
tamination [103]. Elevated concentrations of PAHs, such as chrysene and benzo(a)anthra-
cene, in water and sediment samples near the Constanța complex indicate significant local
pollution. Additionally, atmospheric deposition from combustion sources in the port ar-
eas exacerbates the spread of these contaminants.
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The extent of PAH contamination across Constanța and its satellite ports suggests
that local sources, particularly petroleum activities, are primary contributors to the overall
pollution load. The PAHs from these anthropogenic activities not only affect local marine
ecosystems but may also be transported to adjacent coastal areas and further offshore by
currents, as reflected by the elevated levels detected in open marine waters.

Figure 11. Total content of polycyclic aromatic hydrocarbons (PAHs) in waters (µg/L) and sediments
(µg/g), 2020–2022.

Our data showed that anthracene and phenanthrene are the predominant PAHs in-
troduced into the Danube–Black Sea transition zone [104], especially in front of the Sulina
and Sf. Gheorghe branches, up to the 30 m isobath. In contrast, the offshore marine waters
in the northern region are primarily characterized by the presence of fluorene and fluo-
ranthene. The coastal anthropogenic influence is marked by a more complex PAH mix-
ture, with phenanthrene and anthracene being the predominant components. The areas
adjacent to petroleum activities (the Petromidia refinery and OMV platforms) are charac-
terized by the presence of pyrene and, to some extent, fluorene. Notably, naphthalene is
present in the southern shelf waters, while naphthalene and fluorene are almost exclu-
sively found in the offshore zone. The maximum value observed was solely due to the
presence of chrysene and benzo(a)anthracene at the 60 m isobath in the Mangalia area
(Figure 12).
The sources of PAHs could include both natural (petrogenic/biogenic) and anthropo-
genic (pyrolytic) origins [105]. Our observations suggest influences from both fossil fuel
combustion, as well as direct petrogenic contributions. However, certain areas exhibit a
clear anthropogenic influence characterized by a predominance of pyrolytic PAHs, such
as the Gura Buhaz profile near the Petromidia refinery and the Midia port, the Constanța
and Mangalia port areas, and the northern shelf waters, specifically in the 70–200 m bath-
ymetric strip. Conversely, the southern shelf and offshore waters are dominated by petro-
genic PAHs (Figure 13).
Sediments near the mouth of the Danube show the significant accumulation of pyro-
lytic PAHs, with phenanthrene, fluoranthene, and benzo(a)pyrene being the primary com-
pounds. The anthropogenic influence of the petroleum terminal and the Midia and
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Constanța ports is also reflected in the presence of petrogenic PAHs. In contrast, sediments
in the southern sector are almost exclusively polluted with pyrolytic hydrocarbons, such
as phenanthrene and benzo(a)pyrene. Additionally, the influence of pyrolytic PAHs is ev-
ident in the offshore marine sediments ( Figure 14; Figure 15).

Figure 12. Percentage contribution of individual compounds to the average content of PAHs in sea-
water (µg/L), 2020–2022.

Figure 13. Percentage contribution of petrogenic/biogenic and pyrolytic hydrocarbons to the aver-
age content of PAHs in the waters (µg/L), 2020–2022.
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Figure 14. Percentage contribution of individual compounds to the average content of PAHs in sed-
iments (µg/g), 2020–2022.

Figure 15. Percentage contribution of petrogenic/biogenic and pyrolytic hydrocarbons to the aver-
age content of PAHs in sediments (µg/g), 2020–2022.

4.3. Heavy metals (HMs)


HMs pollution in marine environments is a significant concern due to its detrimental
effects on both ecological and human health. The sources of HMs can be categorized as
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natural and anthropogenic origins. Natural sources primarily include geological pro-
cesses such as the weathering of metal-bearing rocks and volcanic eruptions, which con-
tribute trace amounts of the metals essential for marine life [106,107]. However, anthropo-
genic activities have increasingly overshadowed these natural contributions, leading to
elevated levels of HMs in coastal waters and sediments. Major anthropogenic sources in-
clude industrial discharges, agricultural runoff, urban wastewater, and mining activities
[108–111].
The impact of HM pollution is particularly pronounced in coastal areas, where hu-
man activities are concentrated. For instance, studies have shown that HMs such as cad-
mium (Cd), lead (Pb), and mercury (Hg) are often found in high concentrations in sedi-
ments and seawater near industrial zones and urban [112–114].
The bioaccumulation of HMs in marine organisms poses additional risks to human
health. Fish and shellfish, which are vital components of the human diet, can accumulate
harmful levels of metals, leading to potential health risks upon consumption [115–117].
The toxicity of HMs can affect various organs, including the liver and kidneys, and can
lead to long-term health issues [117,118]. Furthermore, the persistence of HMs in the en-
vironment complicates remediation efforts, as these pollutants can remain in ecosystems
for extended periods, continually affecting marine life and human health [119,120].
The concentrations of HMs in Romanian marine waters, determined during 2020–
2022, showed a high degree of variability. The copper distribution in surface waters re-
flects the influence of the Danube on transitional waters, as well as contributions from
other remote sources, indicated by some elevated (extreme) values in the shelf and off-
shore marine waters of the northern sector. Conversely, the offshore waters in the south-
ern sector show significantly lower values compared to coastal waters, particularly those
near port areas. Cadmium exhibits a pronounced gradient from transitional and coastal
waters to shelf and offshore marine waters. Higher lead concentrations were noted in
coastal waters, likely correlated with port activities, shipping, and wastewater treatment
facilities, with these values significantly reduced in offshore marine waters. Nickel, similar
to copper, shows a marked concentration gradient from north to south. In contrast, chro-
mium displays a different distribution pattern from the other elements, with higher con-
centrations in offshore marine waters, implying that other sources, such as atmospheric
deposition, could be contributing to these elevated levels (Figure 16).
In sediments, the distribution of HMs reveals notable spatial variability, influenced
by both natural factors, such as grain size and the organic matter content, [121] and human
activities, including industrial discharges, port operations, and riverine inputs. The ob-
served patterns suggest that areas with finer grain sizes and a higher organic content serve
as repositories for HMs, as these characteristics facilitate the binding and accumulation of
contaminants. The transitional and marine zones of the Romanian Black Sea sector display
consistently higher concentrations of HMs, particularly in areas influenced by the Danube
River. This is evident from the spatial distribution patterns (Figure 17), where sediments
from the northern sector exhibits elevate levels of heavy metals. These areas are charac-
terized by fine-grained sediments, which have a greater surface area for metal adsorption,
and a higher organic matter content that enhances metal binding [60,121]. The Danube’s
extensive catchment area, which passes through industrialized and agricultural regions,
contributes to the elevated HM levels, particularly for copper, cadmium, and lead, which
are commonly associated with both natural and anthropogenic sources.
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Figure 16. Distribution of HMs in surface marine waters, 2020–2022.

Localized peaks in HM concentrations are observed in coastal areas near major ports,
such as Constanța and Mangalia. This is particularly noticeable for cadmium and nickel,
which show distinct spatial patterns. Cadmium concentrations are significantly elevated
near the Constanța port (Figure 17). This can be attributed to industrial discharges and
urban runoff, compounded by the presence of wastewater treatment plants in the vicinity.
Ports often act as a focal point for pollution due to their proximity to high-density urban
areas and the heavy maritime traffic, which can introduce pollutants into the sediment
through various means, including fuel combustion, metal corrosion, and accidental spills.
Nickel concentrations are notably higher in port areas, particularly near Constanța and
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Mangalia (Figure 17), reflecting the influence of port operations, which may include ac-
tivities such as metal handling, shipbuilding, and industrial emissions. Chromium shows
a relatively uniform distribution across coastal and shelf sediments, with higher concen-
trations in transitional waters (Figure 17). This suggests multiple sources of Cr, including
riverine inputs from the Danube and atmospheric deposition. While riverine inputs play
a major role in transitional areas, the widespread presence of Cr in coastal zones points to
long-range transport through atmospheric pathways and diffuse industrial emissions.
Cr’s strong affinity for fine particles and organic matter helps it persist and accumulate in
these sediments over time.

Figure 17. Concentrations of HMs in sediments, 2020–2022.


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The analysis of boxplots representing HM variability across different Marine Report-


ing Units (MRUs) (median values, interquartile ranges, and outliers) supports the inter-
pretation of distribution maps and offers deeper insights into how contamination levels
vary spatially, particularly highlighting the influence of riverine inputs and port activities
(Figure 18). For instance, clear contamination gradients for most elements, with higher
concentrations in transitional areas, or localized outliers near major ports, were confirmed
(Figure 18). In particular, copper, nickel, and lead show the highest concentrations and
variability in transitional waters, with significant outliers also seen in shelf waters,
whereas cadmium shows outliers and higher concentrations in coastal and shelf waters.
Chromium exhibits a more uniform distribution across the MRUs, but with higher con-
centrations and variability in transitional waters, indicated by several outliers (Figure 18).
A limitation of this study is the lack of data on the sediment organic carbon content
and granulometry, which are important factors in understanding the mechanisms behind
heavy metal accumulation. For the purpose of this paper, we relied on literature data to
provide context for the observed spatial distribution patterns [122–128]. Incorporating di-
rect measurements of these parameters would provide a more comprehensive explanation
of the HMs distribution in Romanian Black Sea sediments. Future research should focus
on analyzing the grain size distribution and organic matter content to gain a deeper un-
derstanding of the processes driving heavy metal deposition and accumulation in this re-
gion.
Previous research on Black Sea pollution has emphasized the substantial issue of con-
taminant distribution in the region. These studies have revealed that various factors, in-
cluding hydrodynamic processes, riverine inputs, atmospheric deposition, sediment dy-
namics, and biological processes [129], influence the spatial distribution of pollutants. For
instance, various studies have revealed concerning levels of HMs, particularly in areas
influenced by river runoff and urban discharges [14–16]. Furthermore, the presence of
PAHs, often resulting from industrial activities and oil spills, has been documented in the
region, contributing to the degradation of marine ecosystems [17,18].
PCBs and OCPs have also been identified as significant contaminants. These com-
pounds are known for their resistance to degradation, their capacity to build up within
the food chain and their prolonged negative impacts on ecosystems [20,21]. Research has
shown that the concentrations of pollutants in the Black Sea are affected by multiple fac-
tors, such as water dynamics and human activities, particularly from riverine inputs. A
recent study identified over 80 types of organic pollutants in Black Sea waters, highlight-
ing the extensive contamination faced by this semi-closed marine environment [19].
Our findings are consistent with earlier studies, showing that the spatial distribution
of pollutants in the Black Sea area is shaped by several factors. Coastal areas near urban
centers, industrial zones, and agricultural regions often exhibit higher pollution levels due
to direct discharges and runoff [38,130]. Big rivers like the Danube, Dnieper, Don, Dnie-
ster, and Kızılırmak transport pollutants from inland sources, significantly impacting
coastal waters during periods of high flow [78,131]. The pollution dynamics are further
influenced by the Black Sea’s cyclonic circulation system, which connects the waters of
neighboring countries [132]. This current facilitates the redistribution of pollutants, trans-
porting contaminants across national borders and affecting the entire northwestern and
western sectors of the Black Sea [133]. Hydrodynamic patterns in this system [134] em-
phasize the need for coordinated international efforts in pollution management and mon-
itoring.
Sediment accumulation can also affect benthic organisms and potentially release con-
taminants back into the water column [135–137]. Sedimentation rates influence the dy-
namics of pollution. A notably high sedimentation rate in proximity to the Danube River
delta has been observed, potentially resulting in the accumulation of pollutants within the
sediments [138]. The bioaccumulation of hazardous substances in marine organisms poses
a significant threat to both ecosystem and human health, necessitating robust monitoring
and regulatory frameworks [28,37,139,140].
Sustainability 2024, 16, 9785 38 of 49

Figure 18. HM variability in sediments across different Marine Reporting Units (MRUs).

For the Romanian waters, the Danube River acts as a conduit for pollutants originat-
ing from upstream sources, including industrial activities, agricultural runoff, and urban
wastewater. Ineffective wastewater treatment processes can lead to the release of pollu-
tants into the marine ecosystem [141]. Industrial discharges, both coastal and inland, fur-
ther contribute to the pollutant load [4]. Additionally, airborne pollutants introduced
through atmospheric deposition affect both surface waters and sediments [142]. Also, the
recent intensification of maritime traffic, due to the current regional geopolitical context,
including ships transporting grains to Romanian ports, could represent an additional an-
thropogenic pressure upon the marine environment [101].
Sustainability 2024, 16, 9785 39 of 49

Overall, our study highlights the river’s influence on Romanian Black Sea transitional
waters across various matrices, namely, surface waters, sediments, and biota, affecting a
wide range of pollutants. HMs concentrations, including nickel, lead, copper, and cad-
mium, show a clear decreasing spatial gradient from river mouths toward offshore areas
or the south (Figure 16 Figure 17 Figure 18). Compounds such as DDT and its breakdown
products, along with specific PCB congeners, are detected at elevated concentrations near
the river’s discharge zone (Figure 8; Figure 9). Among PAHs, compounds like anthracene
showed localized exceedances in transitional waters (Figure 12).
Previous assessments found that transitional waters under the influence of the Dan-
ube often do not achieve GES, not only for contamination, but also for the eutrophication
or biodiversity descriptors [2,12,29]. A regional study involving Ukraine, Romania, Bul-
garia and Turkey that evaluated the influence of rivers on the Black Sea underscored the
crucial role of rivers, including the Danube, as major conduits for pollutants such as HMs,
POPs, and nutrients. A notable spatial gradient emerges, with the highest pollution con-
centrations occurring near river mouths, especially in the northwestern Black Sea, and
decreasing offshore [78]. These findings emphasize the importance of sustained monitor-
ing and cooperative regional management to reduce the impact of river-borne pollution
on the Black Sea ecosystem.
The pollution dynamics in the Black Sea are compounded by the complex interplay
of various sources, including atmospheric deposition, riverine inputs, and maritime and
industrial activities [143–145]. A significant contributor to the degradation of the Black Sea
ecosystem is nutrient pollution, primarily originating from agricultural runoff,
wastewater treatment plants, and riverine discharges [146–148]. Excessive nutrient loads,
especially nitrogen and phosphorus, lead to eutrophication, resulting in harmful algal
blooms, hypoxia, and biodiversity loss, which further stress the marine environment [39].
The impacts of nutrient pollution are most evident in coastal and transitional waters,
where agricultural and urban activities dominate [2]. Moreover, the cumulative effects of
tourism, agriculture, and fishing activities further complicate the pollution landscape, ne-
cessitating a coordinated international response to mitigate these challenges [26,149].
In addressing the overall marine environmental quality of the Romanian Black Sea,
our study aligns with key regional assessments, such as the Black Sea Commission (BSC)
State of Environment Report [1], or the ANEMONE [38,77,78] and EMBLAS [149,150] Pro-
jects. These initiatives have consistently underscored the environmental challenges the
Black Sea faces, particularly with eutrophication, pollution, biodiversity loss, and ecosys-
tem degradation. The findings of our study contribute to the understanding of these per-
sistent issues, offering updated insights specific to the Romanian sector and its progress
toward achieving GES, as required by the MSFD. It is important to note that only two
Black Sea countries, Romania and Bulgaria, are EU members and thus required to meet
GES targets under the MSFD, while other countries in the region are not bound by the
same regulations. This creates additional complexity in managing the shared marine en-
vironment. Our study emphasizes the importance of enhancing cross-border cooperation
for sustained monitoring, as highlighted in the ANEMONE [48] and EMBLAS projects, to
effectively address these regional challenges and move toward a healthier and more sus-
tainable Black Sea ecosystem.
While this study primarily focuses on surface waters and surface sediments, future
research should investigate the variability in contaminants with depth, both in sediments
and along the water column. Contaminant concentrations can vary significantly with sed-
iment depth, particularly in areas influenced by riverine sedimentation. Deeper sediment
layers may reveal long-term deposition trends, while resuspension events, due to natural
hydrodynamics or human activities like dredging, could redistribute contaminants into
the water column. Understanding the vertical distribution of contaminants in both sedi-
ments and the water column would provide a more comprehensive view of their long-
term environmental impact. Additionally, future studies should further explore the influ-
ence of the Danube River, given its pivotal role in transporting pollutants into the
Sustainability 2024, 16, 9785 40 of 49

Romanian Black Sea sector. Investigating seasonal variations in river discharge and their
impact on contaminant levels, coupled with a focus on human activities contributing to
riverine pollution, would enhance our understanding of the river’s overall contribution to
regional contamination patterns.

5. Conclusions
This study offers a critical evaluation of pollution levels in the Romanian Black Sea,
focusing on water, sediment, and biota contamination. Key pollutants such as HMs,
PAHs, and POPs were found to exceed regulatory thresholds, particularly near pollution
hotspots. The findings highlight the need for enhanced regulations, regional cooperation,
and better waste management to mitigate ongoing pollution challenges, including off-
shore contamination. By providing new data, especially for offshore areas, and advocating
for improved multi-metric assessment tools, this study significantly contributes to future
Good Environmental Status (GES) evaluations and marine pollution management under
the MSFD framework.
The comprehensive assessment of the contamination status in the Romanian Black
Sea ecosystem highlights significant environmental challenges that remain unresolved.
Our findings indicate that none of the Marine Reporting Units (MRUs) achieved GES un-
der the MSFD, demonstrating persistent contamination across all matrices—water, sedi-
ment, and biota. Critical pollutants, like HMs, POPs, and PAHs, remain a substantial risk
for the health of marine ecosystems. The spatial distribution of pollutants underscores the
need for targeted pollution control efforts, particularly in regions impacted by riverine
inputs, industrial discharges, and urban runoff. The presence of contaminants even in off-
shore waters further indicates that diffuse sources, such as atmospheric deposition and
increased maritime activity, are contributing to the overall pollution burden [101].
While the use of the “one out-all out” (OOAO) approach provided a sound frame-
work for assessing GES, the complexity of marine pollution calls for more advanced meth-
ods [57,73]. By focusing on cumulative impacts rather than isolated exceedances, multi-
metric, indicator-based methods, like the Chemical Status Assessment Tool (CHASE)
[74,76] and Chemical Quality Index (CQI) [75], offer a more nuanced and adaptive frame-
work for assessing chemical status. This integrated approach makes them more useful for
decision-makers, as they better identify contamination hotspots and support targeted en-
vironmental management actions [76]. In future national assessments, we strongly recom-
mend exploring the use of these tools, as they provide a more balanced and realistic eval-
uation of environmental status compared to traditional OOAO [57], allowing for better-
informed and more effective marine protection measures.
Based on the study’s findings and common environmental management practices,
the following strategies to address the problem of pollution are proposed:
1. Enhanced regional cooperation
Given the transboundary nature of pollution in the Black Sea, fostering stronger re-
gional cooperation among bordering nations is critical. This can include:
- Joint monitoring programs: regular joint monitoring initiatives can help track
pollution sources and trends.
- Shared data platforms: developing a regional data-sharing platform to facilitate
the exchange of environmental data can improve understanding and allow for
coordinated response measures.
2. Implementation of advanced pollution control technologies [151–153]
To mitigate industrial discharges and agricultural runoffs, the following technologies
can be recommended:
- Green infrastructure: the construction of wetlands, riparian buffers, and biore-
actors can help filter pollutants like nitrates, phosphates, and heavy metals be-
fore they reach coastal waters [154].
Sustainability 2024, 16, 9785 41 of 49

- Advanced wastewater treatment [155]: upgrading existing wastewater treat-


ment facilities to include technologies like membrane filtration, adsorption, or
advanced oxidation processes could significantly reduce contaminant loads,
particularly POPs and PAHs.
3. Stricter enforcement of existing regulations
- Tightening emission limits: the stricter enforcement of existing pollution control
measures, especially for industries and agricultural sectors, is essential. This
could involve fines for non-compliance and incentives for industries that adopt
cleaner technologies [156].
- Marine traffic management: given the impact of maritime traffic on the pollution
levels (especially PAHs from oil transport), implementing stricter pollution con-
trol regulations for vessels and promoting cleaner fuel alternatives for ships can
help reduce pollution from this source [157,158].
4. Integrated pollution assessment tools
- Expanding the use of integrated multi-metric tools, like the Chemical Status As-
sessment Tool (CHASE) and the Chemical Quality Index (CQI), which are used
in other EU countries and which consider cumulative impacts rather than iso-
lated pollutant exceedances [75,76,159,160]. This approach can provide more
comprehensive environmental assessments and guide more effective manage-
ment actions [161,162].
5. Public and stakeholder engagement [163]
- Community awareness campaigns: raising awareness among local communities
and stakeholders (e.g., industries, farmers, fishermen) regarding pollution
sources and prevention strategies can foster greater compliance and promote
sustainable practices.
- Incentive programs for cleaner practices: offering incentives to industries or ag-
ricultural entities that adopt greener technologies or practices can encourage
pollution reduction at the source [156].
Thus, to address the pressing issue of pollution in the region, it is imperative to
strengthen regulatory frameworks, enhance monitoring and assessment capabilities, fos-
ter regional cooperation, and actively engage the public and stakeholders. The stricter en-
forcement of pollution control regulations, particularly for industrial and urban sources
of contamination, is urgently needed. Expanding long-term monitoring programs to cover
a wider range of contaminants and matrices, along with the adoption of more sophisti-
cated assessment tools, will provide a more accurate understanding of contamination
trends. Given the shared nature of the Black Sea, coordinated efforts between bordering
nations are essential for developing and implementing region-wide strategies to reduce
pollution. Raising awareness about the impacts of marine contamination and involving
local stakeholders in environmental management can foster greater compliance with pol-
lution control measures and promote sustainable practices. By implementing these rec-
ommendations, we can work towards a healthier and more resilient Black Sea ecosystem.
Sustainability 2024, 16, 9785 42 of 49

Author Contributions: Conceptualization, A.O. and V.C.; methodology, A.O.; V.C.; N.D.; D.D. and
E.R.; software, A.O. and V.C.; validation, A.O., V.C., N.D., D.D. and E.R.; formal analysis, A.O., V.C.,
N.D., D.D. and E.R.; investigation A.O., V.C., N.D., D.D. and E.R.; resources, A.O., V.C., N.D., D.D.
and E.R.; data curation, A.O., V.C., N.D., D.D. and E.R.; writing—original draft preparation, A.O.,
V.C. and N.D.; writing—review and editing, A.O. and V.C.; visualization, A.O., V.C. and N.D.; su-
pervision, A.O.; project administration, A.O.; funding acquisition, A.O. All authors have read and
agreed to the published version of the manuscript.
Funding: This manuscript is a result of the Administrative Capacity Operational Program 2014-2020,
priority axis IP12/2018 under project code MySMIS 127598/SIPOCA 608 “Improving the capacity of
the central public authority in the field of marine environment protection in terms of monitoring,
evaluation, planning, implementation and reporting of requirements set out in the Framework Di-
rective Marine Strategy and for integrated coastal zone management” and European Union’s Hori-
zon 2020 research and innovation program HORIZON-CL6-2021-BIODIV-01-04 under grant agree-
ment No. 101059877 “GES4SEAS -Achieving Good Environmental Status for maintaining ecosystem
SErvices, by Assessing integrated impacts of cumulative pressures”
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data belong to the National Institute for Marine Research and
Development “Grigore Antipa” (NIMRD) and can be accessed upon request to
http://www.nodc.ro/data_policy_nimrd.php (accessed on 12 September 2024).
Acknowledgments: The authors would like to extend their sincere gratitude to our colleague Lu-
minita Lazar for her invaluable contributions to this research. Lazar’s expertise in ArcGIS was in-
strumental in the creation of the contamination distribution maps, and her expert advice signifi-
cantly enhanced the quality of the paper.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Krutov, A. (Ed.) BSC State of the Environment of the Black Sea (2009-2014/5); Publications of the Commission on the Protection of
the Black Sea Against Pollution (BSC): Istanbul, Turkey, 2019.
2. Lazar, L.; Vlas, O.; Pantea, E.; Boicenco, L.; Marin, O.; Abaza, V.; Filimon, A.; Bisinicu, E. Black Sea Eutrophication Comparative
Analysis of Intensity between Coastal and Offshore Waters. Sustainability 2024, 16, 5146. https://doi.org/10.3390/su16125146.
3. Daskalov, G.M.; Boicenco, L.; Grishin, A.N.; Lazar, L.; Mihneva, V.; Shlyakhov, V.A.; Zengin, M. Architecture of Collapse: Re-
gime Shift and Recovery in an Hierarchically Structured Marine Ecosystem. Glob. Change Biol. 2017, 23, 1486–1498.
https://doi.org/10.1111/gcb.13508.
4. Lazar, L.; Spanu, A.; Boicenco, L.; Oros, A.; Damir, N.; Bisinicu, E.; Abaza, V.; Filimon, A.; Harcota, G.; Marin, O.; et al. Meth-
odology for Prioritizing Marine Environmental Pressures under Various Management Scenarios in the Black Sea. Front. Mar.
Sci. 2024, 11. https://doi.org/10.3389/fmars.2024.1388877.
5. Lazar, L.; Rodino, S.; Pop, R.; Tiller, R.; D’Haese, N.; Viaene, P.; De Kok, J.-L. Sustainable Development Scenarios in the Danube
Delta—A Pilot Methodology for Decision Makers. Water 2022, 14, 3484. https://doi.org/10.3390/w14213484.
6. Cozzi, S.; Ibáñez, C.; Lazar, L.; Raimbault, P.; Giani, M. Flow Regime and Nutrient-Loading Trends from the Largest South
European Watersheds: Implications for the Productivity of Mediterranean and Black Sea’s Coastal Areas. Water 2018, 11, 1.
https://doi.org/10.3390/w11010001.
7. Bisinicu, E.; Abaza, V.; Boicenco, L.; Adrian, F.; Harcota, G.-E.; Marin, O.; Oros, A.; Pantea, E.; Spinu, A.; Timofte, F.; et al. Spatial
Cumulative Assessment of Impact Risk-Implementing Ecosystem-Based Management for Enhanced Sustainability and Biodi-
versity in the Black Sea. Sustainability 2024, 16, 4449. https://doi.org/10.3390/su16114449.
8. Bat, L.; Öztekin, A.; Şahin, F.; Arıcı, E.; Özsandıkçı, U. An Overview of the Black Sea Pollution in Turkey; Turkish Marine Research
Foundation: Beykoz, Turkey, 2018; Vol. 1;.
9. Bișinicu, E.; Lazăr, L.; Timofte, F. Dynamics of Zooplankton along the Romanian Black Sea Coastline: Temporal Variation, Com-
munity Structure, and Environmental Drivers. Divers. 2023, 15, 1024. https://doi.org/10.3390/d15091024.
10. Bisinicu, E.; Harcota, G.; Lazar, L. Interactions between Environmental Factors and the Mesozooplankton Community from the
Romanian Black Sea Waters. Turk. J. Zool. 2023, 47, 202–215. https://doi.org/10.55730/1300-0179.3133.
11. Lazar, L.; Boicenco, L.; Pantea, E.; Timofte, F.; Vlas, O.; Bișinicu, E. Modeling Dynamic Processes in the Black Sea Pelagic Habi-
tat—Causal Connections between Abiotic and Biotic Factors in Two Climate Change Scenarios. Sustainability 2024, 16, 1849.
https://doi.org/10.3390/su16051849.
Sustainability 2024, 16, 9785 43 of 49

12. Bișinicu, E.; Boicenco, L.; Pantea, E.; Timofte, F.; Lazăr, L.; Vlas, O. Qualitative Model of the Causal Interactions between Phyto-
plankton, Zooplankton, and Environmental Factors in the Romanian Black Sea. Phycology 2024, 4, 168–189.
https://doi.org/10.3390/phycology4010010.
13. Akoglu, E. Ecological Indicators Reveal Historical Regime Shifts in the Black Sea Ecosystem. PeerJ 2023, 11, e15649.
https://doi.org/10.7717/peerj.15649.
14. Ulger, S.; Higano, Y. A Preliminary Study to Improve the Water Quality in the Black Sea: Turkish Black Sea Basin. Stud. Reg. Sci.
2001, 32, 353–367. https://doi.org/10.2457/srs.32.353.
15. Jitar, O.; Teodosiu, C.; Nicoara, M.; Plavan, G. Study of Heavy Metal Pollution and Bioaccumulation in the Black Sea Living
Environment. Environ. Eng. Manag. J. 2013, 12, 271–276. https://doi.org/10.30638/eemj.2013.032.
16. Bucse, A.; Parvulescu, O.; Vasiliu, D.; Lupașcu, N.; Voica, C. Levels of Heavy Metal Concentrations in M. Galloprovincialis
Mollusks Species from NW Black Sea (Romania). Bull. Series B 2021, 83, 51–60.
17. Chiţescu, C.L.; Ene, A.; Geana, E.-I.; Vasile, A.M.; Ciucure, C.T. Emerging and Persistent Pollutants in the Aquatic Ecosystems
of the Lower Danube Basin and North West Black Sea Region—A Review. Appl. Sci. 2021, 11, 9721.
https://doi.org/10.3390/app11209721.
18. Damir, N.-A.; Coatu, V.; Pantea, E.D.; Galațchi, M.; Botez, E.; Birghilă, S. Assessment of Polycyclic Aromatic Hydrocarbons
Content in Marine Organisms of Commercial Interest from the Romanian Black Sea Coast. Polycycl. Aromat. Compd. 2022, 42,
7595–7606. https://doi.org/10.1080/10406638.2021.2006243.
19. Pavlovska, M.; Solomenko, I.; Prekrasna, I.E. Ecological Evaluation of Aquatic Microorganisms Role in Xenobiotics Transfor-
mation with the Reference to the Black Sea. Biol. Syst. Theory Innov. 2021, 12. https://doi.org/10.31548/biologiya2021.01.007.
20. Denga, Y.M.; Mykhailenko, V.I.; Oleynik, Y.V.; SafranovТ. А Peculiarities of Pollution by Some Persistent Organic Pollutants of
the Marine Environment of the Northwestern Part of the Black Sea. Visnyk VN Karazin Kharkiv Natl. Univ. Ser. Ecol. 2020.
https://doi.org/10.26565/1992-4259-2020-23-01.
21. Danilov, D.; Dediu, L.; Damir, N.A.; Coatu, V.; Lazar, L. Screening for Organic Pollutants in the Black Sea Turbot (Scophthalmus
Maeoticus). Fishes 2023, 8, 265. https://doi.org/10.3390/fishes8050265.
22. Directive 2008/56/EC of the European Parliament and of the Council of 17 June 2008 Establishing a Framework for Community
Action in the Field of Marine Environmental Policy (Marine Strategy Framework Directive). Off. J. Eur. Union 2008, 164,
25.6.2008, p. 19–40.
23. Golumbeanu, M.; Oros, A.; Nenciu, M.; Zavatarelli; M.; Drago, A. Contribution of Environmental Indices in Meeting the Objec-
tives and Principles of the Marine Strategy Framework Directive (MSFD). J. Environ. Prot. Ecol. 2014, 15, 1130–1138.
24. Kudelsky, A.V. Global Geoenvironmental Problems: Black Sea Basin. Water Resour. 2011, 38, 849–858.
https://doi.org/10.1134/S0097807811070086.
25. Orhon, D. Evaluation of the Impact from the Black Sea on the Pollution of the Marmara Sea. Water Sci. Technol. 1995, 32, 191–
198. https://doi.org/10.2166/wst.1995.0231.
26. Strokal, M.; Strokal, V.; Kroeze, C. The Future of the Black Sea: More Pollution in over Half of the Rivers. Ambio 2023, 52, 339–
356. https://doi.org/10.1007/s13280-022-01780-6.
27. Bakan, G.; Büyükgüngör, H. The Black Sea. Mar. Pollut. Bull. 2000, 41, 24–43. https://doi.org/10.1016/S0025-326X(00)00100-4.
28. Damir, N.; Coatu, V.; Danilov, D.; Lazăr, L.; Oros, A. From Waters to Fish: A Multi-Faceted Analysis of Contaminants’ Pollution
Sources, Distribution Patterns, and Ecological and Human Health Consequences. Fishes 2024, 9, 274.
https://doi.org/10.3390/fishes9070274.
29. Boicenco, L.; Abaza, V.; Anton, E.; Bisinicu, E.; Buga, L.; Coatu, V.; Damir, N.; Diaconeasa, D.; Dumitrache, C.; Filimon, A.; et al.
Studiu Privind Elaborarea Raportului Privind Starea Ecologică a Ecosistemului Marin Marea Neagră Conform Cerintelor Art.
17 Ale Directivei Cadru Strategia Pentru Mediul Marin (2008/56/EC). 2018. Available online: https://www.mme-
diu.ro/app/webroot/uploads/files/Studiu_raport_MSFD-2024.pdf (accessed on 29 September 2024).
30. Oros, A. Monitoring and Assessment of Heavy Metals in the Romanian Black Sea Ecosystem during 2006-2018, in the Context
of Marine Strategy Framework Directive (MSFD) 2008/56/EC Implementation. Cercet. Mar.—Rech. Mar. 2019, 49, 8–33.
https://doi.org/10.55268/CM.2019.49.8.
31. Commission Decision (EU) 2017/848 of 17 May 2017 Laying down Criteria and Methodological Standards on Good Environ-
mental Status of Marine Waters and Specifications and Standardised Methods for Monitoring and Assessment, and Repealing
Decision 2010/477/EU. Off. J. Eur. Union 2017, 25, 18.5.2017, p. 43–74.
32. Tornero Alvarez, M.; Hanke, G.; Oros, A.; Ramšak, A.; Duffek, A.; Wernersson, A.; Ausili, A.; Maggi, C.; Robinson, C.; Tiganus,
D.; et al. Review of the Commission Decision 2010/477/EU Concerning MSFD Criteria for Assessing Good Environmental Status: De-
scriptor 8 Concentrations of Contaminants Are at Levels Not Giving Rise to Pollution Effects. EUR 27464; Publications Office of the
European Union: Luxembourg, 2015.
33. Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 Establishing a Framework for Commu-
nity Action in the Field of Water Policy. Off. J. Eur. Union 2000, 327, 22.12.2000, p. 1–73.
34. Commission Regulation (EU) 2023/915 of 25 April 2023 on Maximum Levels for Certain Contaminants in Food and Repealing
Regulation (EC) No 1881/2006. Off. J. Eur. Union 2023, 119, 5.5.2023, p. 103–157.
35. Tornero, V.; Boschetti, S.; Hanke, G. Marine Strategy Framework Directive—Review and Analysis of EU Member States’ 2018 Reports—
Descriptor 8: Contaminants in the Environment—Descriptor 9: Contaminants in Seafood. EUR 30659 EN; Publications Office of the
European Union: Luxembourg, 2021. https://doi.org/10.2760/621757.
Sustainability 2024, 16, 9785 44 of 49

36. Directive 2013/39/EU of the European Parliament and of the Council of 12 August 2013 Amending Directives 2000/60/EC and
2008/105/EC as Regards Priority Substances in the Field of Water Policy. Off. J. Eur. Union 2013, 226, 24.8.2013, p. 1–17.
37. Oros, A.; Pantea, E.-D.; Ristea, E. Heavy Metal Concentrations in Wild Mussels Mytilus Galloprovincialis (Lamarck, 1819) dur-
ing 2001–2023 and Potential Risks for Consumers: A Study on the Romanian Black Sea Coast. Sci 2024, 6, 45.
https://doi.org/10.3390/sci6030045.
38. Lazar, L. (Ed.) ANEMONE Deliverable 2.2 “Anthropogenic Pressures and Impacts on the Black Sea Coastal Ecosystem”; Editura CD
Press: București, Romania, 2021; ISBN 978-606-528-529-3.
39. Cociasu, A.; Varga, L.; Lazar, L.; Vasiliu, D. Recent Data Concerning the Evolution of the Eutrophication Level Indicators in
Romanian Seawater. J. Environ. Prot. Ecol. 2009, 10, 701–731.
40. Grasshoff, K.; Kremling, K.; Ehrhardt, M. (Eds.) Methods of Seawater Analysis, 3rd ed.; Willey-VCH: Weinheim, Germany, 1999;
ISBN: 978-3-527-61399-1.
41. UNEP/IOC/IAEA. Manual for the Geochemical Analysis of Marine Sediments and Suspended Particulate Matter; Reference Methods
for Marine Pollution Studies No. 63; United Nations Environment Programme: Nairobi, Kenya, 1995.
42. UNEP/FAO/IOC/IAEA. Guidelines for Monitoring Chemical Contaminants in the Sea Using Marine Organisms; Reference Methods
for Marine Pollution Studies No. 63; United Nations Environment Programme: Nairobi, Kenya, 1993.
43. IAEA-MEL Training Manual on the Measurement of Heavy Metals in Environmental Samples; IAEA-MEL: Monaco (Monte
Carlo), 1999.
44. IAEA-MEL. Training Manual on the Measurement of Organochlorine and Petroleum Hydrocarbons in Environmental Samples;
IAEA-MEL: Monaco (Monte Carlo), 1995.
45. TIBCO Statistica; Version 14.0.1.25; TIBCO Software Inc.: Palo Alto, CA, USA, 2023.
46. Schlitzer, R. Ocean Data View. Available online: https://odv.awi.de (accessed on 11 July 2024).
47. ESRI ArcGIS Desktop, Version 10.7; Environmental Systems Research Institute (ESRI), Redlands, California, USA, 2019.
48. ANEMONE Deliverable 1.3 “Black Sea Monitoring and Assessment Guideline”; Todorova, V., Ed.; Editura CD Press: București, Ro-
mania, 2021; ISBN 978-606-528-527-9.
49. 2019 Updated Audit Trail of OSPAR EACs and Other Assessment Criteria Used to Distinguish above and below Thresholds.
2020. Available online: https://www.ospar.org/documents?v=43066 (accessed on 29 September 2024).
50. Long, E.; Morgan, L. The Potential for Biological Effects of Sediment-Sorbed Contaminants Tested in the National Status and Trends
Program; US Department of Commerce, National Oceanic and Atmospheric Administration, National Ocean Service: Silver
Spring, MD, USA, 1991; Volume 52.
51. Long, E.R.; Field, L.J.; MacDonald, D.D. Predicting Toxicity in Marine Sediments with Numerical Sediment Quality Guidelines.
Environ. Toxicol. Chem. 1998, 17, 714–727. https://doi.org/10.1002/etc.5620170428.
52. Buchman, M.F. Screening Quick Reference Tables (SQuiRTs); In NOAA OR & R Report; NOS (National Ocean Service), ORR
(Office of Response and Restoration): Silver Spring, MD, USA, 2008.
53. Long, E.R.; Macdonald, D.D.; Smith, S.L.; Calder, F.D. Incidence of Adverse Biological Effects within Ranges of Chemical Con-
centrations in Marine and Estuarine Sediments. Environ. Manag. 1995, 19, 81–97. https://doi.org/10.1007/BF02472006.
54. Order No. 161/2006 for the Approval of the Regulation on the Classification of Surface Water Quality for Determining the Eco-
logical Status of Water Bodies (in Romanian). In Official Gazette of Romania, Bucharest, Romania, no. 511, June 13, 2006.; 2006.
55. Lamine, I.; Chahouri, A.; Mghili, B.; Moukrim, A.; Ait Alla, A. Do the Individual and Population-Level Traits of Donax Trun-
culus Reflect the Effects of Metal Contamination in Aquatic Environments? Mar. Environ. Res. 2023, 191, 106134.
https://doi.org/10.1016/j.marenvres.2023.106134.
56. Heiskanen, A.-S.; van de Bund, W.; Cardoso, A.C.; Nõges, P. Towards Good Ecological Status of Surface Waters in Europe—
Interpretation and Harmonisation of the Concept. Water Sci. Technol. 2004, 49, 169–177. https://doi.org/10.2166/wst.2004.0447.
57. Borja, Á.; Rodríguez, J.G. Problems Associated with the One-out, All-out’ Principle, When Using Multiple Ecosystem Compo-
nents in Assessing the Ecological Status of Marine Waters. Mar. Pollut. Bull. 2010, 60, 1143–1146. https://doi.org/10.1016/j.mar-
polbul.2010.06.026.
58. Order No. 147 of December 29, 2004 for the Approval of Veterinary Health and Food Safety Standards Regarding Pesticide
Residues in Products of Animal and Non-Animal Origin and Veterinary Drug Residues in Products of Animal Origin (in Ro-
manian). In Official Gazette of Romania, Bucharest, Romania, no. 143, February 17, 2005; 2004.
59. Vorkamp, K.; Bossi, R.; Bester, K.; Bollmann, U.E.; Boutrup, S. New Priority Substances of the European Water Framework
Directive: Biocides, Pesticides and Brominated Flame Retardants in the Aquatic Environment of Denmark. Sci. Total Environ.
2014, 470–471, 459–468. https://doi.org/10.1016/j.scitotenv.2013.09.096.
60. Oros, A.; V. Coatu; D. Secrieru; D. Țigănuș; D. Vasiliu; H. Atabay; C. Beken; L. Tolun; S. Moncheva; L. Bat Results of the Assess-
ment of the Western Black Sea Contamination Status in the Frame of the MISIS Joint Cruise. Cercet. Mar. 2016, 46, 61–81.
61. Secrieru, D.; Secrieru, A. Heavy Metal Enrichment of Man-Made Origin of Superficial Sediment on the Continental Shelf of the
North-Western Black Sea. Estuar. Coast. Shelf Sci. 2002, 54, 513–526. https://doi.org/10.1006/ecss.2000.0671.
62. Vignati, D.A.L.; Secrieru, D.; Bogatova, Y.I.; Dominik, J.; Céréghino, R.; Berlinsky, N.A.; Oaie, G.; Szobotka, S.; Stanica, A. Trace
Element Contamination in the Arms of the Danube Delta (Romania/Ukraine): Current State of Knowledge and Future Needs.
J. Environ. Manag. 2013, 125, 169–178. https://doi.org/10.1016/j.jenvman.2013.04.007.
63. Gheorghe, O.A.; Secrieru, D.; Bondar, C.; Szobotka, Ş.; Laura, D.; STĂNESCUI; Opreanu, G.; Florin, D.; Pojar, I.; Lower Danube
River: Characterization of Sediments and Pollutants. Geo-EcoMar 2015, 21, 19–34.
Sustainability 2024, 16, 9785 45 of 49

64. Omar, M.B.; Mendiguchía, C.; Er-Raioui, H.; Marhraoui, M.; Lafraoui, G.; Oulad-Abdellah, M.K.; García-Vargas, M.; Moreno,
C. Distribution of Heavy Metals in Marine Sediments of Tetouan Coast (North of Morocco): Natural and Anthropogenic
Sources. Environ. Earth Sci. 2015, 74, 4171–4185. https://doi.org/10.1007/s12665-015-4494-4.
65. Özbay, Ö. Assessment of Heavy Metal Pollution in Coastal Surface Sediments of the Mersin Bay, Northeastern Mediterranean
Sea. Int. J. Environ. Sci. Technol. 2024, 21, 875–884. https://doi.org/10.1007/s13762-023-05196-x.
66. Ravisankar, R.; Sivakumar, S.; Chandrasekaran, A.; Kanagasabapathy, K.V.; Prasad, M.V.R.; Satapathy, K.K. Statistical Assess-
ment of Heavy Metal Pollution in Sediments of East Coast of Tamilnadu Using Energy Dispersive X-Ray Fluorescence Spec-
troscopy (EDXRF). Appl. Radiat. Isot. 2015, 102, 42–47. https://doi.org/10.1016/j.apradiso.2015.03.018.
67. Gu, Y.-G.; Gao, Y.-P. An Unconstrained Ordination- and GIS-Based Approach for Identifying Anthropogenic Sources of Heavy
Metal Pollution in Marine Sediments. Mar. Pollut. Bull. 2019, 146, 100–105. https://doi.org/10.1016/j.marpolbul.2019.06.008.
68. Probst, W.N. A Generic Aggregation Approach to Account for Statistical Uncertainty When Combining Multiple Assessment
Results. Ecol. Indic. 2017, 73, 686–693. https://doi.org/10.1016/j.ecolind.2016.10.027.
69. Coatu, V.; Damir, N.; Oros, A.; Boicenco, L.; Lazar, L. Revised Methodology of Black Sea Chemical Status Under Water Frame-
work Directive. J. Environ. Prot. Ecol. 2018, 19, 601–608.
70. Zacharias, I.; Liakou, P.; Biliani, I. A Review of the Status of Surface European Waters Twenty Years after WFD Introduction.
Environ. Process. 2020, 7, 1023–1039. https://doi.org/10.1007/s40710-020-00458-z.
71. Moe, S.J.; Lyche Solheim, A.; Soszka, H.; Gołub, M.; Hutorowicz, A.; Kolada, A.; Picińska-Fałtynowicz, J.; Białokoz, W. Inte-
grated Assessment of Ecological Status and Misclassification of Lakes: The Role of Uncertainty and Index Combination Rules.
Ecol. Indic. 2015, 48, 605–615. https://doi.org/10.1016/j.ecolind.2014.08.018.
72. Caroni, R.; Bund, W.; Clarke, R.T.; Johnson, R.K. Combination of Multiple Biological Quality Elements into Waterbody Assess-
ment of Surface Waters. Hydrobiologia 2012, 704, 437–451. https://doi.org/10.1007/s10750-012-1274-y.
73. Borja, A.; Elliott, M.; Andersen, J.H.; Berg, T.; Carstensen, J.; Halpern, B.S.; Heiskanen, A.-S.; Korpinen, S.; Lowndes, J.S.S.; Mar-
tin, G.; et al. Overview of Integrative Assessment of Marine Systems: The Ecosystem Approach in Practice. Front. Mar. Sci. 2016,
3. https://doi.org/10.3389/fmars.2016.00020.
74. Andersen, J.H.; Murray, C.; Larsen, M.M.; Green, N.; Høgåsen, T.; Dahlgren, E.; Garnaga-Budrė, G.; Gustavson, K.; Haarich, M.;
Kallenbach, E.M.F.; et al. Development and Testing of a Prototype Tool for Integrated Assessment of Chemical Status in Marine
Environments. Environ. Monit. Assess. 2016, 188, 115. https://doi.org/10.1007/s10661-016-5121-x.
75. Maggi, C.; Berducci, M.T.; Di Lorenzo, B.; Lomiri, S.; Venti, F. Integrated Chemical Status of the Italian Marine Waters Sensu
Descriptor 8 of the Marine Strategy Framework Directive. Front. Mar. Sci. 2022, 9. https://doi.org/10.3389/fmars.2022.1006595.
76. Andersen, J.H.; Caetano, M.; Grouhel-Pellouin, A.; Harvey, E.T.; Reker, J.; Murray, C.J. Mapping of Contamination Problem
Areas in Europe’s Seas Using a Multi-Metric Indicator-Based Assessment Tool. Front. Mar. Sci. 2022, 9.
https://doi.org/10.3389/fmars.2022.1037914.
77. Lazar, L. (Ed.) ANEMONE Deliverable 2.3 “Black Sea State of Environment Based on ANEMONE Joint Cruise”; Editura CD Press:
Bucharest, Romania, 2021.
78. Lazar, L. (Ed.) ANEMONE Deliverable 2.1 “Impact of the Rivers on the Black Sea Ecosystem”; Editura CD Press: Bucharest, Romania,
2021; ISBN 978-606-528-528-6.
79. Apaydın, A.; Kabaoğlu, H.; Apaydın, G.; Şirin, M.; Cengiz, E.; Köksal, O.K.; Baltaş, H.; Tıraşoğlu, E. Evaluation of Ecological
Risk, Source, and Spatial Distribution of Some Heavy Metals in Marine Sediments in the Middle and Eastern Black Sea Region,
Turkey. Environ. Sci. Pollut. Res. 2022, 29, 7053–7066. https://doi.org/10.1007/s11356-021-16017-4.
80. Shypotilova, O.; Kozhanov, A.; Lohinova, L.; Lohinov, O. The Problem of the Black Sea Pollution in Odessa Region of Ukraine.
IOP Conf. Ser. Earth Environ. Sci. 2021, 915, 012008. https://doi.org/10.1088/1755-1315/915/1/012008.
81. Mityagina, M.I. Assessment of Surface Oil Pollution Risks of the Southeastern Black Sea Based on Long-Term Satellite Data. In
Proceedings of the Remote Sensing of the Ocean, Sea Ice, Coastal Waters, and Large Water Regions 2019, Strasbourg, France, 9–
10 September 2009; Bostater, C.R., Neyt, X., Viallefont-Robinet, F., Eds.; SPIE: Cergy-Pontoise, France, 2019; p. 46.
82. Akkoyunlu, A. Land-Based Pollution on the Black Sea along the Turkish Shoreline. J. Mar. Sci. Res. Dev. 2018, 08.
https://doi.org/10.4172/2155-9910.1000248.
83. Geyikçi, F.; Büyükgüngör, H. Monitoring of Organochlorine Pesticides in the Surface Waters from Mid-Black Sea Region, Tur-
key. Environ. Monit. Assess. 2011, 173, 127–137. https://doi.org/10.1007/s10661-010-1376-9.
84. Masood, N.; Zakaria, M.P.; Halimoon, N.; Aris, A.Z.; Magam, S.M.; Kannan, N.; Mustafa, S.; Ali, M.M.; Keshavarzifard, M.;
Vaezzadeh, V.; et al. Anthropogenic Waste Indicators (AWIs), Particularly PAHs and LABs, in Malaysian Sediments: Application
of Aquatic Environment for Identifying Anthropogenic Pollution. Mar. Pollut. Bull. 2016, 102, 160–175.
https://doi.org/10.1016/j.marpolbul.2015.11.032.
85. Davis, E.; Walker, T.R.; Adams, M.; Willis, R.; Norris, G.A.; Henry, R.C. Source Apportionment of Polycyclic Aromatic Hydro-
carbons (PAHs) in Small Craft Harbor (SCH) Surficial Sediments in Nova Scotia, Canada. Sci. Total Environ. 2019, 691, 528–537.
https://doi.org/10.1016/j.scitotenv.2019.07.114.
86. Modiga, A.; Gasparotti, C.; Rusu, L.; Popescu, G. Analysis of the Main Operations and the Characteristics of the Environmental
Matrix at the Romanian Harbours in the Black Sea. In Proceedings of the 3rd International Conference on Traffic and Transport
Engineering (ICTTE), publisher: City Net Scientific Research Center, Guimarães, Portugal, 4–7 September 2016; Cokorilo, O.,
Ed.; 2016; pp. 291–296.
Sustainability 2024, 16, 9785 46 of 49

87. Mostert, M.M.R.; Ayoko, G.A.; Kokot, S. Application of Chemometrics to Analysis of Soil Pollutants. TrAC Trends Anal. Chem.
2010, 29, 430–445. https://doi.org/10.1016/j.trac.2010.02.009.
88. Jordan, R.E.; Cejas, M.J.; Costa, H.J.; Sauer, T.C.; McWilliams, L.S. PAH Source Differentiation between Historical MGP and
Significant Urban Influences for Sediments in San Francisco Bay. Mar. Pollut. Bull. 2021, 166, 112248.
https://doi.org/10.1016/j.marpolbul.2021.112248.
89. Stout, S.A.; Emsbo-Mattingly, S.D. Concentration and Character of PAHs and Other Hydrocarbons in Coals of Varying Rank—
Implications for Environmental Studies of Soils and Sediments Containing Particulate Coal. Org. Geochem. 2008, 39, 801–819.
https://doi.org/10.1016/j.orggeochem.2008.04.017.
90. Aravind Kumar, J.; Krithiga, T.; Sathish, S.; Renita, A.A.; Prabu, D.; Lokesh, S.; Geetha, R.; Namasivayam, S.K.R.; Sillanpaa, M.
Persistent Organic Pollutants in Water Resources: Fate, Occurrence, Characterization and Risk Analysis. Sci. Total Environ. 2022,
831, 154808. https://doi.org/10.1016/j.scitotenv.2022.154808.
91. Zanoletti, A.; Bontempi, E. Editorial: Urban Runoff of Pollutants and Their Treatment. Front. Environ. Chem. 2023, 4.
https://doi.org/10.3389/fenvc.2023.1151859.
92. Ashraf, M.A. Persistent Organic Pollutants (POPs): A Global Issue, a Global Challenge. Environ. Sci. Pollut. Res. 2017, 24, 4223–
4227. https://doi.org/10.1007/s11356-015-5225-9.
93. Cindoruk, S.S.; Tasdemir, Y. The Investigation of Atmospheric Deposition Distribution of Organochlorine Pesticides (OCPs) in
Turkey. Atmos. Environ. 2014, 87, 207–217. https://doi.org/10.1016/j.atmosenv.2014.01.008.
94. ICPDR. Revision and Update of The Danube Study “Integrating and Editing New Scientific Results in Climate Change Research
and the Resulting Impacts on Water Availability to Revise the Existing Adaptation Strategies in the Danube River Basin”. 2018.
Available online: https://www.icpdr.org/resources/climate-change-adaptation-update-danube-study (accessed on 29 Septem-
ber 2024).
95. Shamma, S.; Dawood, M.; El-Nahrery, E.M.A.; Shahat, A.; El-Sayed, M.M.H.; Hegazy, M.N.; Sewilam, H.N.; Shoeib, T.; Ab-
delnaser, A. Seasonal Dynamics and Ecological Risks of Organochlorine Pesticides in Kafrelsheikh-Egypt: Implications for
Aquatic Ecosystems and Public Health. Environ. Adv. 2024, 16, 100547. https://doi.org/10.1016/j.envadv.2024.100547.
96. Martyniuk, C.J.; Mehinto, A.C.; Denslow, N.D. Organochlorine Pesticides: Agrochemicals with Potent Endocrine-Disrupting
Properties in Fish. Mol. Cell Endocrinol. 2020, 507, 110764. https://doi.org/10.1016/j.mce.2020.110764.
97. Yang, X.; Wang, L.; Zhang, A.; Liu, X.; Bidegain, G.; Zong, H.; Guan, C.; Song, M.; Qu, L.; Huang, W.; et al. Levels, Sources and
Potential Risks of Polychlorinated Biphenyls and Organochlorine Pesticides in Sediments of Qingduizi Bay, China: Does Devel-
oping Mariculture Matter? Front. Mar. Sci. 2019, 6, 602. https://doi.org/10.3389/fmars.2019.00602.
98. Carvalho, F.P. Pesticides, Environment, and Food Safety. Food Energy Secur. 2017, 6, 48–60. https://doi.org/10.1002/fes3.108.
99. Scully-Engelmeyer, K.; Granek, E.F.; Nielsen-Pincus, M.; Lanier, A.; Rumrill, S.S.; Moran, P.; Nilsen, E.; Hladik, M.L.; Pillsbury,
L. Exploring Biophysical Linkages between Coastal Forestry Management Practices and Aquatic Bivalve Contaminant Expo-
sure. Toxics 2021, 9, 46. https://doi.org/10.3390/toxics9030046.
100. Brubaker, W.W.; Hites, R.A. OH Reaction Kinetics of Gas-Phase α- and γ-Hexachlorocyclohexane and Hexachlorobenzene.
Environ. Sci. Technol. 1998, 32, 766–769. https://doi.org/10.1021/es970650b.
101. Shchiptsov, O.A.; Goncharov, O.Y. European Research Project on the State of Pollution in the Black Sea «Black Sea SIERRA»:
Mission and Participation of Ukrainian Oceanographers. Geofiz. Zhurnal 2023, 45, 162–171.
https://doi.org/10.24028/gj.v45i6.293315.
102. Mai, C.; Theobald, N.; Hühnerfuss, H.; Lammel, G. Persistent Organochlorine Pesticides and Polychlorinated Biphenyls in Air
of the North Sea Region and Air-Sea Exchange. Environ. Sci. Pollut. Res. 2016, 23, 23648–23661. https://doi.org/10.1007/s11356-
016-7530-3.
103. Pocora, A.; Purcarea, A.A.; Nicolae, F.; Cotorcea, A. Modelling and Simulation of Oil Spills in Coastal Waters. IOP Conf. Ser.
Earth Environ. Sci. 2018, 172, 012012. https://doi.org/10.1088/1755-1315/172/1/012012.
104. Constantinescu, A.M.; Tyler, A.N.; Stanica, A.; Spyrakos, E.; Hunter, P.D.; Catianis, I.; Panin, N. A Century of Human Interven-
tions on Sediment Flux Variations in the Danube-Black Sea Transition Zone. Front. Mar. Sci. 2023, 10, 1068065.
https://doi.org/10.3389/fmars.2023.1068065.
105. Ponce-Velez, G.; Botello, A.V.; Diaz-Gonzalez, G. Organic and Inorganic Pollutants in Marine Sediments from Northern and
Southern Continental Shelf of the Gulf of Mexico. Int. J. Environ. Pollut. 2006, 26, 295. https://doi.org/10.1504/IJEP.2006.009113.
106. Yümün, Z.Ü.; Aslıyüksek, H.; Yentür, M.M.; Önce, M. Measurement of Heavy Metal Concentrations of Marine Sediments in
Yalova Section of Marmara Sea by LIBS Method And Evaluation of Pollution By Principal Component Analysis. Cihannüma
Teknol. Fen Mühendislik Bilim. Akad. Derg. 2022, 1, Issue: 1, 101 - 117,. https://doi.org/10.55205/joctensa.11202233.
107. Ali, M.M.; Hossain, D.; Al-Imran, A.; Khan, M.S.; Begum, M.; Osman, M.H. Environmental Pollution with Heavy Metals: A
Public Health Concern. In Heavy Metals—Their Environmental Impacts and Mitigation; IntechOpen: London, UK, 2021.
108. González-Fernández, D.; Garrido-Pérez, M.C.; Nebot-Sanz, E.; Sales-Márquez, D. Source and Fate of Heavy Metals in Marine
Sediments from a Semi-Enclosed Deep Embayment Subjected to Severe Anthropogenic Activities. Water Air Soil. Pollut. 2011,
221, 191–202. https://doi.org/10.1007/s11270-011-0782-0.
109. Asih, A.S.; Zamroni, A.; Alwi, W.; Sagala, S.T.; Putra, A.S. Assessment of Heavy Metal Concentrations in Seawater in the Coastal
Areas around Daerah Istimewa Yogyakarta Province, Indonesia. Iraqi Geol. J. 2022, 55, 14–22.
https://doi.org/10.46717/igj.55.1B.2Ms-2022-02-18.
Sustainability 2024, 16, 9785 47 of 49

110. Wang, J. Heavy Metal Pollution of Surface Sediments In The Northern Waters Of The Abandoned Yellow River Delta In Jiangsu
Province Of China And Ecological Risk Assessment. Appl. Ecol. Environ. Res. 2019, 17.
https://doi.org/10.15666/aeer/1706_1486714882.
111. Wang, X.; Feng, H.; Ma, H. Assessment of Metal Contamination in Surface Sediments of Jiaozhou Bay, Qingdao, China. Clean
2007, 35, 62–70. https://doi.org/10.1002/clen.200600022.
112. Ganesan, C.M.; Chinnaraju, C.; Lavanya, A.R.; Prabakar, K. Occurrence, Spatial Distribution and Ecological Impact of Heavy
Metals in Rivers, Lakes and Marine Environments of Tamil Nadu, India. Asian J. Chem. 2022, 34, 3037–3047.
https://doi.org/10.14233/ajchem.2022.24024.
113. Wang, H.; Fan, Z.; Kuang, Z.; Yuan, Y.; Liu, H.; Huang, H. Heavy Metals in Marine Surface Sediments of Daya Bay, Southern
China: Spatial Distribution, Sources Apportionment, and Ecological Risk Assessment. Front. Environ. Sci. 2021, 9.
https://doi.org/10.3389/fenvs.2021.755873.
114. Sun, X.; Li, B.-S.; Liu, X.-L.; Li, C.-X. Spatial Variations and Potential Risks of Heavy Metals in Seawater, Sediments, and Living
Organisms in Jiuzhen Bay, China. J. Chem. 2020, 2020, 1–13. https://doi.org/10.1155/2020/7971294.
115. Venkateswarlu, V.; Venkatrayulu, C. Bioaccumulation of Heavy Metals in Edible Marine Fish from Coastal Areas of Nellore,
Andhra Pradesh, India. GSC Biol. Pharm. Sci. 2020, 10, 018–024. https://doi.org/10.30574/gscbps.2020.10.1.0244.
116. Pund, A.; Kurhe, A. A Review on Heavy Metals Impact and Marine Molluscs. Int. J. Multidiscip. Res. Growth Eval. 2023, 4, 535–
538. https://doi.org/10.54660/.IJMRGE.2023.4.3.535-538.
117. Vajargah, M.F.; Azar, H. Investigating the Effects of Accumulation of Lead and Cadmium Metals in Fish and Its Impact on
Human Health. J. Aquac. Mar. Biol. 2023, 12, 209–213. https://doi.org/10.15406/jamb.2023.12.00376.
118. He, B.; Yun, Z.; Shi, J.; Jiang, G. Research Progress of Heavy Metal Pollution in China: Sources, Analytical Methods, Status, and
Toxicity. Chin. Sci. Bull. 2013, 58, 134–140. https://doi.org/10.1007/s11434-012-5541-0.
119. Morankar, N.H.; Kurhe, A.R. An Overview of the Impact of Heavy Metal Accumulation on Marine Molluscs. Int. J. Multidiscip.
Res. Growth Eval. 2023, 4, 760–764. https://doi.org/10.54660/.IJMRGE.2023.4.5.760-764.
120. Bandara, K.R.V.; Manage, P.M. Heavy Metal Contamination in the Coastal Environment and Trace Level Identification; In Ma-
rine Pollution-Recent Developments; IntechOpen: London, UK, 2023.
121. Lazar, L.; Gomoiu, M.T.; Boicenco, L.; Vasiliu, D. Total Organic Carbon (TOC) of the Surface Layer Sediments Covering the
Seafloor of the Romanian Black Sea Coast. Geoecomarina 2012, 18, 121–132.
122. Ovsyany, E.I.; Kotelyanets, E.A.; Orekhova, N.A. Arsenic and Heavy Metals in the Bottom Sediments of the Balaklava Bay (Black
Sea). Phys. Oceanogr. 2009, 19, 254–266. https://doi.org/10.1007/s11110-009-9048-4.
123. Bat, L.; Ozkan, E.Y.; Buyukisik, H.B.; Oztekin, H.C. Assessment of Metal Pollution in Sediments along Sinop Peninsula of the
Black Sea. Int. J. Mar. Sci. 2017, 7, 205–213. https://doi.org/10.5376/ijms.2017.07.0022.
124. Orekhova, N.A.; Ovsyany, E.I.; Gurov, K.I.; Popov, M.A. Organic Matter and Grain-Size Distribution of the Modern Bottom
Sediments in the Balaklava Bay (the Black Sea). Phys. Oceanogr. 2019, 25, 479–488. https://doi.org/10.22449/1573-160X-2018-6-
479-488.
125. Jessen, G.L.; Lichtschlag, A.; Ramette, A.; Pantoja, S.; Rossel, P.E.; Schubert, C.J.; Struck, U.; Boetius, A. Hypoxia Causes Preser-
vation of Labile Organic Matter and Changes Seafloor Microbial Community Composition (Black Sea). Sci. Adv. 2017, 3,
e1601897. https://doi.org/10.1126/sciadv.1601897.
126. Marin, D.; Petrișoaia, S.; Spînu, A.; Mateescu, R.; Diaconeasa, D.; Vespremeanu, E. Assessment of the Geomorphological and
Sedimentological Changes in Mamaia Sector after the Implementation of the Coastal Protection Measures. Cercet. Mar.—Rech.
Mar. 2022, 52, 6–16. https://doi.org/10.55268/CM.2022.52.6.
127. Ozkan, E.Y.; Buyukisik, B. Geochemical and Statistical Approach for Assessing Heavy Metal Accumulation in the Southern
Black Sea Sediments. Ekoloji 2012, 21, 11–24. https://doi.org/10.5053/ekoloji.2012.832.
128. Panin, N.; Jipa, D. Danube River Sediment Input and Its Interaction with the North-Western Black Sea. Estuar. Coast. Shelf Sci.
2002, 54, 551–562. https://doi.org/10.1006/ecss.2000.0664.
129. Kennish, M.J. Pollution Impacts on Marine Biotic Communities; CRC Press: Boca Raton, FL, USA, 2020; ISBN 9781003069003.
130. Fazio, F.; D’Iglio, C.; Capillo, G.; Saoca, C.; Peycheva, K.; Piccione, G.; Makedonski, L. Environmental Investigations and Tissue
Bioaccumulation of Heavy Metals in Grey Mullet from the Black Sea (Bulgaria) and the Ionian Sea (Italy). Animals 2020, 10, 1739.
https://doi.org/10.3390/ani10101739.
131. Bakan, G.; Boke Ozkoc, H.; Tulek, S.; Cuce, H. Integrated Environmental Quality Assessment of Kizilirmak River and Its Coastal
Environment. Turk. J. Fish. Aquat. Sci. 2010, 10, 453–462. https://doi.org/10.4194/trjfas.2010.0403.
132. Oguz, T.; Ivanov, L.; Besiktepe, Ş.T. Circulation and Hydrographic Characteristics of the Black Sea during July 1992. In Proceed-
ings of the NATO TU Black Sea Project Ecosystem Jodeling as a Management Tool for the Black Sea, Odessa, Ukraine, 15–19
June 1997; ZORI ROSSII: Ukraine, 1997; Volume 47, pp. 69–91.
133. Capet, A.; Barth, A.; Beckers, J.-M.; Marilaure, G. Interannual Variability of Black Sea’s Hydrodynamics and Connection to
Atmospheric Patterns. Deep Sea Res. Part II Top. Stud. Oceanogr. 2012, 77–80, 128–142. https://doi.org/10.1016/j.dsr2.2012.04.010.
134. Markova, N.V.; Bagaev, A.V. The Black Sea Deep Current Velocities Estimated from the Data of Argo Profiling Floats. Phys.
Oceanogr. 2016, 3, 23–35. https://doi.org/10.22449/1573-160X-2016-3-23-35.
135. Unsal, M. Lead Pollution and Its Sources along the Turkish Coast of the Black Sea. Mediterr. Mar. Sci. 2001, 2, 33.
https://doi.org/10.12681/mms.265.
Sustainability 2024, 16, 9785 48 of 49

136. Korablina, I.V.; Barabashin, T.O.; Katalevsky, N.I. Heavy Metals in the Bottom Sediments of the Black Sea Northwestern Shelf
in Recent Years. Phys. Oceanogr. 2021, 28, 549–566. https://doi.org/10.22449/1573-160X-2021-5-549-566.
137. Ozseker, K.; Eruz, C. Pollution Assessment of Toxic Metals in Representative Limnetic Ecosystem Sediments in the Southeastern
Black Sea, Turkey. Clean 2017, 45, 1700407. https://doi.org/10.1002/clen.201700407.
138. Ayçik, G.A.; Çetaku, D.; Erten, H.N.; Salihoglu, I. Dating of Black Sea Sediments from Romanian Coast Using Natural 210 Pb and
Fallout 137Cs. J. Radioanal. Nucl. Chem. 2004, 259, 177–180. https://doi.org/10.1023/B:JRNC.0000015825.67418.18.
139. Bat, L. One Health: The Interface Between Fish and Human Health. Curr. World Environ. 2019, 14, 355–357.
https://doi.org/10.12944/CWE.14.3.04.
140. Bat, L.; Yardım, Ö.; Öztekin, A.; Arıcı, E. Assessment of Heavy Metal Concentrations in Scophthalmus Maximus (Linnaeus,
1758) from the Black Sea Coast: Implications for Food Safety and Human Health. J. Hazard. Mater. Adv. 2023, 12, 100384.
https://doi.org/10.1016/j.hazadv.2023.100384.
141. Muftuoglu, A.E. Transportation of Pollutants of the Danube River into the (Western) Black Sea. Asian J. Chem. 2013, 25, 5013–
5018. https://doi.org/10.14233/ajchem.2013.14279.
142. Castro-Jiménez, J.; Berrojalbiz, N.; Pizarro, M.; Dachs, J. Organophosphate Ester (OPE) Flame Retardants and Plasticizers in the
Open Mediterranean and Black Seas Atmosphere. Environ. Sci. Technol. 2014, 48, 3203–3209. https://doi.org/10.1021/es405337g.
143. Akdemir, T.; Dalgic, G. The Impact of the Marine Sewage Outfalls on the Sediment Quality: The Black Sea and the Marmara
Case. Saudi J. Biol. Sci. 2021, 28, 238–246. https://doi.org/10.1016/j.sjbs.2020.09.055.
144. Shtereva, G.P.; Dzhurova, B.S.; Nikolova, T.S. Contamination of Sediments in Varna Lake and Varna Bay. Water Sci. Technol.
2004, 50, 317–320. https://doi.org/10.2166/wst.2004.0343.
145. Berkun, M.; Aras, E. Wastewater and Waste-Generated Pollution at the Southeastern Black Sea Region. Environ. Eng. Sci. 2007,
24, 778–789. https://doi.org/10.1089/ees.2006.0129.
146. Artioli, Y.; Friedrich, J.; Gilbert, A.J.; McQuatters-Gollop, A.; Mee, L.D.; Vermaat, J.E.; Wulff, F.; Humborg, C.; Palmeri, L.;
Pollehne, F. Nutrient Budgets for European Seas: A Measure of the Effectiveness of Nutrient Reduction Policies. Mar. Pollut.
Bull. 2008, 56, 1609–1617. https://doi.org/10.1016/j.marpolbul.2008.05.027.
147. McQuatters-Gollop, A.; Gilbert, A.J.; Mee, L.D.; Vermaat, J.E.; Artioli, Y.; Humborg, C.; Wulff, F. How Well Do Ecosystem Indi-
cators Communicate the Effects of Anthropogenic Eutrophication? Estuar. Coast. Shelf Sci. 2009, 82, 583–596.
https://doi.org/10.1016/j.ecss.2009.02.017.
148. Strokal, M.; Kroeze, C. Nitrogen and Phosphorus Inputs to the Black Sea in 1970–2050. Reg Env. Change 2013, 13, 179–192.
https://doi.org/10.1007/s10113-012-0328-z.
149. Alygizakis, N.; Giannakopoulos, T.; Τhomaidis, N.S.; Slobodnik, J. Detecting the Sources of Chemicals in the Black Sea Using
Non-Target Screening and Deep Learning Convolutional Neural Networks. Sci. Total Environ. 2022, 847, 157554.
https://doi.org/10.1016/j.scitotenv.2022.157554.
150. Kharytonova, Y.V.; Nabokin, M.V.; Mgeladze, M.M.; Vadachkoria, P.A.; Dyadichko, V.G. Current State and Long-Term Changes
in the Mesozooplankton Community of the Ukrainian and Georgian Parts of the Black Sea as Indicators of Its Ecological Status.
Biosyst. Divers. 2021, 29, 47–58. https://doi.org/10.15421/012107.
151. Cui, L.L. Solution of Landscape Water Pollution in Residential. Adv. Mat. Res. 2012, 461, 822–825.
https://doi.org/10.4028/www.scientific.net/AMR.461.822.
152. Weng, C.-H. Water Environment and Recent Advances in Pollution Control Technologies. Environ. Sci. Pollut. Res. 2022, 29,
12462–12464. https://doi.org/10.1007/s11356-021-17392-8.
153. Himabindu, V.; Bhramara, P. Pollution Control and Energy Advanced Technologies. Environ. Sci. Pollut. Res. 2016, 23, 9249–
9250. https://doi.org/10.1007/s11356-016-6698-x.
154. Lu, Y.T.; Chen, P.; Zhu, J.H.; Xu, S.Q.; Gao, J. Empirical Analysis on Pollution Control Effects Decomposition of Environmental
Protection Investments. Adv. Mat. Res. 2013, 726–731, 1400–1404. https://doi.org/10.4028/www.scientific.net/AMR.726-731.1400.
155. Qu, J.; Fan, M. The Current State of Water Quality and Technology Development for Water Pollution Control in China. Crit. Rev.
Environ. Sci. Technol. 2010, 40, 519–560. https://doi.org/10.1080/10643380802451953.
156. Coria, J. Environmental Crises’ Regulations, Tradable Permits and the Adoption of New Technologies. Resour. Energy Econ.
2011, 33, 455–476. https://doi.org/10.1016/j.reseneeco.2010.08.001.
157. Micheli, F.; Halpern, B.S.; Walbridge, S.; Ciriaco, S.; Ferretti, F.; Fraschetti, S.; Lewison, R.; Nykjaer, L.; Rosenberg, A.A. Cumu-
lative Human Impacts on Mediterranean and Black Sea Marine Ecosystems: Assessing Current Pressures and Opportunities.
PLoS ONE 2013, 8, e79889. https://doi.org/10.1371/journal.pone.0079889.
158. Kim, E.; Cho, H.; Kim, N.; Kim, E.; Ryu, J.; Park, H. Sensitive Resource and Traffic Density Risk Analysis of Marine Spill Acci-
dents Using Automated Identification System Big Data. J. Mar. Sci. Appl. 2020, 19, 173–181. https://doi.org/10.1007/s11804-020-
00138-2.
159. Borja, A.; Berg, T.; Gundersen, H.; Hagen, A.G.; Hancke, K.; Korpinen, S.; Leal, M.C.; Luisetti, T.; Menchaca, I.; Murray, C.; et al.
Innovative and Practical Tools for Monitoring and Assessing Biodiversity Status and Impacts of Multiple Human Pressures in
Marine Systems. Environ. Monit. Assess. 2024, 196, 694. https://doi.org/10.1007/s10661-024-12861-2.
160. Lehtonen, K.K.; Sundelin, B.; Lang, T.; Strand, J. Development of Tools for Integrated Monitoring and Assessment of Hazardous
Substances and Their Biological Effects in the Baltic Sea. Ambio 2014, 43, 69–81. https://doi.org/10.1007/s13280-013-0478-3.
Sustainability 2024, 16, 9785 49 of 49

161. Cinnirella, S.; Graziano, M.; Pon, J.; Murciano, C.; Albaigés, J.; Pirrone, N. Integrated Assessment of Chemical Pollution in the
Mediterranean Sea: Driver-Pressures-State-Welfare Analysis. Ocean. Coast. Manag. 2013, 80, 36–45. https://doi.org/10.1016/j.oce-
coaman.2013.02.022.
162. Bowen, R.E.; Depledge, M.H. Rapid Assessment of Marine Pollution (RAMP). Mar. Pollut. Bull. 2006, 53, 631–639.
https://doi.org/10.1016/j.marpolbul.2006.09.002.
163. Järvelä, J.; Sorsa, V.-P.; Spicer, A. Silent Steering: How Public Actors Indirectly Influence Private Stakeholder Engagement. Bus.
Soc. 2024, Advance online publication. https://doi.org/10.1177/00076503241274056.

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