Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution

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Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
water
Article
Environmental Conditions and the Fish Stocks Situation in the
Black Sea, between Climate Change, War, and Pollution
Victorita Radulescu

                                          Hydraulics, Hydraulic Machinery and Environmental Engineering Department, University Politehnica of
                                          Bucharest, Splaiul Independentei 313, 060042 Bucharest, Romania; vradul4@gmail.com; Tel.: +40-745076494

                                          Abstract: Climate change, pollution, capture, invasive species, and the war from Ukraine have
                                          a significant impact on the environment and fish populations in the Black Sea. In June last year,
                                          on the Romanian and Bulgarian seashore, large amounts of algae, dead fish, and jellyfish were
                                          discovered. The ongoing depletion of fish stocks necessitates extensive research, concerning their
                                          living conditions, reproduction, population, and migration. This paper starts by presenting the
                                          environmental conditions for air, sediment, and water up to 60 m, based on direct monitoring and
                                          measurements realized between 2014 and 2020. The recent war has affected the environmental
                                          conditions of the sea, especially near Snake Island and Crimea Peninsula, well known for fish
                                          reproduction. A dedicated paragraph presents the sources of water pollution, with direct effects on
                                          eutrophication, fish reproduction, and their populations. The appearance and development of some
                                          invasive species, which influence the local fish populations, are also illustrated. All these new factors
                                          associated with the capture quotas are responsible for decreasing the number of fish species and their
                                          populations in the Black Sea. Finally, some discussions are mentioned, which are necessary to be
                                          followed in order to restore the fish stocks.

                                          Keywords: biodiversity; environmental monitoring; marine biodiversity; marine pollution;
                                          water monitoring

Citation: Radulescu, V.                   1. Introduction
Environmental Conditions and the
                                               With an area of 461,000 km2 and a volume of 540,000 km3 , the Black Sea is considered
Fish Stocks Situation in the Black Sea,
                                          deep, with a maximum depth of 2212 m. Its characteristics make it unique in Europe [1],
between Climate Change, War, and
                                          being practically a closed sea, communicating only with the Sea of Azov in the north
Pollution. Water 2023, 15, 1012.
https://doi.org/10.3390/w15061012
                                          through the Kerch Strait, and with the Mediterranean Sea to the southwest via the Bospho-
                                          rus and Dardanelles Straits [2]. Compared with other seas, the Black Sea has distinct
Academic Editors: Jun Yang and            natural conditions, with a stratified structure of water composition. Unlike anoxic deep
Adriano Sfriso                            water, surface water is rich in oxygen and nutrients. There is practically no exchange of
Received: 10 January 2023                 substances between these two layers, affecting the diversity of living organisms, being
Revised: 22 February 2023                 lower in species and number than in the Mediterranean Sea [3,4]. The shallow surface layer
Accepted: 2 March 2023                    has medium–high salinity. It has decreased significantly in recent decades due to a large
Published: 7 March 2023                   influx of fresh water from large rivers such as the Danube, Dnieper, Dniester, and Don.
                                               The Black Sea has strategic and political influence, representing the east border of the
                                          EU (European Union) and NATO (North Atlantic Treaty Organization Alliance). Bounded
                                          to the west by two EU member states, Romania and Bulgaria, and in the rest by four non-EU
Copyright:    © 2023 by the author.
                                          states, Ukraine, Russia, Georgia, and Turkey, the Black Sea became a conflict zone due to the
Licensee MDPI, Basel, Switzerland.
                                          Russia–Ukraine war. Three of these countries are also NATO members: Turkey, Bulgaria,
This article is an open access article
                                          and Romania [5,6]. The Black Sea is important for Russia because it represents a direct
distributed under the terms and
                                          connection with the Mediterranean Sea and, further, with the Atlantic Ocean. It ensures
conditions of the Creative Commons
                                          the transport of goods from Russia to the rest of the world throughout the year. The war
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
                                          affects life in the Black Sea. The pipeline Turck Stream, with the protocol signed in 2016,
4.0/).
                                          started its first deliveries through Turkey to Bulgaria in 2020, and the Blue Stream pipelines

Water 2023, 15, 1012. https://doi.org/10.3390/w15061012                                                       https://www.mdpi.com/journal/water
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
Water 2023, 15, 1012                                                                                            2 of 22

                       (protocol signed in 2002), with its first deliveries achieved in 2003 to Turkey, connect Russia
                       with other countries through the Black Sea [7,8]. These pipelines, due to their recorded
                       accidents, have affected the environment in these areas.
                            To maintain the environment and the living conditions of the Black Sea, all states
                       surrounding the Black Sea must respect the signed protocols for good neighborliness. The
                       actual Convention consists of four protocols: the Protocol on the Protection of the Black
                       Sea Marine Environment Against Pollution from Land-Based Sources (LBS Protocol), the
                       Protocol on the Protection of the Black Sea Marine Environment Against Pollution by
                       Dumping, the Protocol on Cooperation in Combating Pollution of the Black Sea Marine
                       Environment by Oil and Other Harmful Substances in Emergency Situations, and The Black
                       Sea Biodiversity and Landscape Conservation Protocol (CBD Protocol) [9–11].
                            Unfortunately, the Black Sea is nowadays the most polluted sea in Europe. Among the
                       principal causes, a few are be mentioned below:
                       -    Uncontrolled spills of oil and residual substances from shipyards and ports;
                       -    Nitrite and nitrate compounds transported by rivers from agricultural lands;
                       -    Bottles and plastic bags, deposited garbage near the seashore;
                       -    Effects induced by war over various environmental aspects: the air, sediments,
                            and water;
                       -    Different substances are discharged, due to the improper functioning of sewage
                            treatment plants placed near the maritime coasts [12–15].
                             This paper analyzes the principal sources of pollution and their effects on the ecosys-
                       tem, and fish development and distribution in the medium and long term. Up to 10–15 years
                       ago, the sea was teeming with life, including birds, specific vegetation, shell and mussel,
                       fish, and mammals, such as dolphins and seals. This marine ecosystem is more complex
                       than other seas due to its specific structure. Its protection is more difficult for scien-
                       tists [16,17]. The salty waters, from the Bosphorus Strait, go to the bottom of the sea, while
                       fresh water from the main rivers, containing agricultural fertilizer and sewage runoff,
                       remains at the surface.
                             In the warm season, these substances cause a rapid and excessive bloom. They affect
                       the oxygen concentration in the water, with a high impact on the entire ecosystem. The
                       lack of mixing between these two layers of water, of which nearly 90% is oxygen-depleted,
                       limits the number of marine species that live in the Black Sea. Bacteria consume the organic
                       matter from this oxygen-free environment (dead plants or fish), producing hydrogen
                       sulfide—H2 S [18,19]. The Black Sea is nowadays the largest H2 S reserve in the world,
                       necessitating permanent monitoring. The implemented environmental regulations are
                       inefficient without constant surveillance.
                             Other problems refer to the current economic and political conditions in the area. The
                       large sturgeon populations in the beginning of the 20th century put black roe on the tables
                       of each fisherman working in the Black Sea.
                             Nowadays, excessive fishing and increased maritime transport have produced the
                       extinction of four of the seven species of sturgeon found once in the Black Sea. The
                       cliffs from the Crimea Peninsula provided, not long ago, a safe refuge for fish, birds,
                       and marine mammals. After the fights of 2014 and due to the mine explosions from last
                       year, associated with the increased transport of commercial ships, many fish and marine
                       mammals retreated to the rock habitats in Bulgaria and Turkey [20]. However, another
                       issue has appeared. The intense development of tourist resorts in both countries in these
                       areas has reduced these habitats even more. Anchovy stocks, once the main catch in the sea,
                       have been massively reduced in the last two decades [21]. Recent hostilities from Ukraine
                       have stopped previous efforts to repopulate some species. Currently, around the Crimean
                       peninsula, 20 km offshore, are Russian waters, where no one knows if the international rules
                       regarding environmental protection, marine life conditions, and fish quotas are respected.
                       The increased Russian and NATO naval exercises have restricted some areas of the Black
                       Sea to civil traffic, including the scientific teams that conduct environmental monitoring
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
Water 2023, 15, 1012                                                                                           3 of 22

                       and surveillance of marine life. Under these conditions, the most recent data recorded and
                       used in this paper were recorded at the end of 2020.
                            As tensions rose, the military ships’ utilization of sonar harmed fish migrations the
                       most. Many species have changed their traditional spawning route, especially near the
                       Ukrainian ports of Odessa and Mykolaiv. Military equipment affects fish life, causing
                       them to leave their usual nesting or foraging areas. Because they can no longer locate the
                       proper places, they have difficulty securing their food and habitat. Last year, many of these
                       animals died near the shore. The worst part is that the environmental monitoring of water
                       quality and living conditions can no longer be realized in many areas.
                            The paper analyzes, in the beginning, the principal causes that have affected the Black
                       Sea ecosystem in the last years, based on the systematic measurements and monitoring
                       realized between 2014 and 2020. The explosive growths of algae in the northern part of the
                       Black Sea, and invasive species of marine fauna, affect the local fish stocks. A few causes
                       affecting endangered fish species are illustrated, based on the recorded measurements
                       for the sediment structure and composition, water quality, and fish captures. A special
                       paragraph is dedicated to some threatened species currently on the verge of extinction if
                       urgent measures to protect them or their living and reproduction zones are not taken.
                            Some measures are proposed for protecting the environment, based on these ob-
                       servations and measurements, as well as the surveillance of fishing quotas, for saving
                       endangered species, and for the restoration of the fish stock, at least in those areas without
                       military exercises that affect wildlife living conditions.
                            The presented results were mostly obtained through direct measurements collected
                       from 2014 to 2020. In 2020, I was part of a research team that collected samples of sedi-
                       ments, water, and biological structure, from the Black Sea. The rest of the data present,
                       by comparison from the previous period 2014–2020, other recorded values, used in order
                       to analyze the evolution of these significant parameters. Some data are reported by other
                       countries, to the Black Sea Commission—BSC.

                       2. Materials and Methods
                             The Romanian Black Sea coastline is 245 km long, from Musura Bay, with the border
                       with Ukraine in the north and the Bulgarian border to the south. Two commercial ports,
                       Tulcea and Constanta, and two shipyards, Mangalia and Navodari, are in this area. The
                       ports are well-known for maritime traffic, due to the Danube–Black Sea channel, which
                       allows the quick transport of different merchandise. These ports were overcrowded last
                       year due to the high volume of ships carrying cereals, oil, and other products from Ukraine
                       to the rest of Europe. The shipyards, also known for the production of commercial ships
                       and their repair, were in great demand last year.
                             A special observation should be made for this area. Many small earthquakes have
                       been recorded recently near the border with Bulgaria. The most recent and significant was
                       in April 2020, with a magnitude of 4.3 on the Richter scale. After that, some small deep
                       currents of fresh water appeared, with a small flow rate but a continuous one. In time, they
                       modified the seashore, causing coastal erosion, with collapsed cliffs.
                             Besides these natural factors, new problems have arisen due to industrial development.
                       Commercial transport, much more intensive in the last year, affects the environmental
                       conditions. Some invasive species from the Mediterranean Sea have colonized the Black
                       Sea and affect the local fauna. Water eutrophication, associated with massive fish catches,
                       mainly by the Turkish, Georgian, and Russian vessels, influences the fish population, which
                       has decreased significantly in the last few years. In addition, the war also perturbs marine
                       life and the environment.
                             Some responsible factors will be next investigated. The main, specific fish characteris-
                       tics of the Black Sea that have been affected by these new conditions will also be presented.
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
icant risks not only for the health of coastal residents but also for the entire environment.
                       To assure good living conditions for people and the marine ecosystem, we must first an‐
                       alyze each responsible factor, starting with air quality, sediment characteristics, and espe‐
                       cially the water parameters. The principal sources of pollution, including effects induced
                       by massive nutrient discharge, ports’ activities, municipal waste production, and inten‐
Water 2023, 15, 1012
                       sive maritime transport, are all responsible for the actual situation in the Black Sea.4 All              of 22

                       these factors impact the biological diversity, trophic chains, appearance and development
                       of non‐indigenous species, and finally, endemic fish and crustacean stocks. A brief presen‐
                         2.1. Main
                       tation        Causes
                                of the mainoffishthe species
                                                     Environmental
                                                              is also Degradation
                                                                      illustrated. Many of them are nowadays on the red
                       list asClimate
                                endangered     species.
                                         change and human activity have a major impact on the marine ecosystem.
                         The large-scale eutrophication of water due to nutrients brought by rivers, the infiltration of
                       2.1.1.  The Air and
                         oil residues,   Quality
                                              waste from human or industrial activities, has produced microbiological
                         and Based
                              chemicalon contamination
                                           the Black Sea in     the water, sediments,
                                                             Collaboration     Agreement andimplementation,
                                                                                               even air. They create     significant
                                                                                                                   riparian   states
                         risks  not only   for  the  health  of  coastal  residents  but  also  for the entire
                       constantly monitor air and water quality. Figure 1a,b illustrates the number of monitoringenvironment.      To
                         assure  good   living   conditions   for people   and  the marine   ecosystem,     we  must
                       vessels and the measuring points by country, according to the last report of the Black Sea      first analyze
                         each responsible
                       Commission       [22]. factor, starting with air quality, sediment characteristics, and especially
                         the water    parameters.
                              Air pollution            Theby
                                               is caused    principal
                                                               natural,sources    of pollution,
                                                                         industrial, or different including    effects
                                                                                                    local factors,  suchinduced
                                                                                                                           as:     by
                         massive nutrient discharge, ports’ activities, municipal waste production, and intensive
                       ‐      Natural sources: volcanic eruptions, earthquakes, rock erosion, pollen scattering;
                         maritime transport, are all responsible for the actual situation in the Black Sea. All these
                       ‐      Anthropogenic sources, such as industrial activities, thermoelectric power plants, or
                         factors impact the biological diversity, trophic chains, appearance and development of non-
                              car traffic;
                         indigenous species, and finally, endemic fish and crustacean stocks. A brief presentation
                       ‐      Recently, other factors were associated, such as bomb explosions, the presence of
                         of the main fish species is also illustrated. Many of them are nowadays on the red list as
                              many battle vessels, bomb explosions, etc.
                         endangered species.
                              Generally, dust, industrial gases, or the unpleasant odors of rotting products or waste
                         2.1.1.
                       are  theThe   Air Quality
                                 primary    causes of air pollution. Sizes of the dust particles or residual gas elements
                       from economic
                               Based on the Blackare
                                           activities      also
                                                         Sea     important parameters.
                                                             Collaboration     AgreementMainly,       the concentrations
                                                                                             implementation,        riparianofstates
                                                                                                                                SO2
                       and    NO2 in monitor
                         constantly    port areas air determine   air pollution.
                                                      and water quality.    FigureThe
                                                                                    1a,bdust  concentration
                                                                                         illustrates  the numberin cities  refers to
                                                                                                                     of monitoring
                       the   suspended
                         vessels  and theparticles
                                            measuring  PMpoints
                                                           10 (Particulate
                                                                   by country,matter  10 μm)toand
                                                                                 according       the PM
                                                                                                     last 2.5. Excessive
                                                                                                          report            concen‐
                                                                                                                  of the Black   Sea
                       trations   have an
                         Commission          impact on the environment.
                                         [22].

                       (a)                                                                     (b)
                       Figure
                        Figure1.1.Surveillance
                                   Surveillanceininthe
                                                    theBlack
                                                        BlackSea:
                                                              Sea:(a)
                                                                   (a)Number
                                                                      Numberofofmonitoring
                                                                                monitoringvessels;
                                                                                           vessels;(b)
                                                                                                    (b)The
                                                                                                        Themeasurement
                                                                                                           measurement
                       points from  the western   part.
                        points from the western part.

                             Air pollution is caused by natural, industrial, or different local factors, such as:
                        -     Natural sources: volcanic eruptions, earthquakes, rock erosion, pollen scattering;
                        -     Anthropogenic sources, such as industrial activities, thermoelectric power plants, or
                              car traffic;
                        -     Recently, other factors were associated, such as bomb explosions, the presence of many
                              battle vessels, bomb explosions, etc.
                             Generally, dust, industrial gases, or the unpleasant odors of rotting products or waste
                        are the primary causes of air pollution. Sizes of the dust particles or residual gas elements
                        from economic activities are also important parameters. Mainly, the concentrations of SO2
                        and NO2 in port areas determine air pollution. The dust concentration in cities refers to the
                        suspended particles PM 10 (Particulate matter 10 µm) and PM 2.5. Excessive concentrations
                        have an impact on the environment.
                             Sulfur dioxide (SO2 ), carbon dioxide, NOx (nitrogen oxides), solid lead, benzene,
                        carbon monoxide, ozone, arsenic, Cd, Hg, and Ni are the main monitoring parameters
                        of air quality. On the Romanian coast, five fixed stations monitor air parameters, such as
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
Water 2023, 15, 1012                                                                                          5 of 22

                       CO, benzene, PM 10, SO2 , NOx , As, PM 2.5, Cd, NO2 , and Ni levels in the areas of Tulcea,
                       Navodari, Mamaia, Constanta, and Mangalia. The direction and intensity of the wind, air
                       temperature, and precipitation play important roles in the transmission of particles that can
                       pollute the Black Sea. The recorded values are used to create databases that are registered
                       hourly, and reported daily or monthly. Based on them, the risk areas are determined.
                             In the chapter Results, the month of May 2020 is mentioned, as an example of the
                       measured values for wind direction, air temperature, and amount of precipitation. Heavy
                       metal particles (HM), Persistent Organic Pollutants (POP), Cd, Pb, Hg, and benzopyrene-
                       B(a)P levels were measured during 2015–2020. For the year 2021, no more centralized
                       databases have been created. In the Results chapter, some obtained results obtained up
                       to 2020, which are associated with some remarks based on the performed measurements,
                       are illustrated.

                       2.1.2. Pollutants in the Bottom Sediments
                            The Black Sea’s unique characteristics make it vulnerable to environmental conditions.
                       The almost complete absence of tides prevents the dilution of contaminants, favoring the
                       natural phenomenon of sedimentation. The movement of water masses between the Black
                       Sea’s two main layers is almost absent. European legislation establishes environmental
                       quality standards only for contaminants in seawater and biota. There are no established
                       threshold values for sediments. On the Romanian coast, systematic measurements are
                       realized at different depths and locations to prevent sediment pollution. Each sample is
                       measured and analyzed optically, physically, and chemically.

                       Content of PAH—Polycyclic Aromatic Hydrocarbon
                            In recent decades, there has been a focus on the content of PAHs and heavy metals.
                       According to the Black Sea Commission (BSC) analysis, seabed sediments can be classified
                       into three categories based on the Total PAH-TPAH content:
                       -    Slightly polluted: TPAH < 250 g/kg;
                       -    Polluted: TPAH = 250–500 g/kg;
                       -    Highly polluted: TPAH > 500 g/kg.
                            The degree is calculated as the ratio of “technical-Fl ” PAH from industrial and hu-
                       man activities and “natural-Fy ” PAH. The PAH analysis from Romania, 2020, reveals the
                       presence of 11 dangerous organic contaminants in marine sediments: naphthalene, ace-
                       naphthylene, fluorene, acenaphthene, phenanthrene, anthracene, fluoranthene, pyrene,
                       benzo(a)anthracene, and chrysene. The Results chapter also illustrates the reported values
                       for 2020, from Romania, Turkey, Bulgaria, and Ukraine, at three time intervals: May, June,
                       and July. For the Romanian coast, the total content of the 11 PAHs (µg/kg) found in
                       sediments is also mentioned.
                            According to the BSC regulations, the following sources of emissions in the environ-
                       ment are estimated:
                       -    If the ratio Fl /(Fl + Fy ) < 0.4, pollution is of petroleum origin;
                       -    Values 0.4–0.5, pollution caused by combustion products of liquid fuel or oil;
                       -    Values > 0.5 indicate pollution caused by the combustion of coal or wood.
                            Sediment samples were processed according to internal standards. An accelerated sol-
                       vent was used on the pressure extraction unit (PLE) with a mixture of hexane/dichloromethane/
                       methanol (60%/20%/20%) in the chemistry laboratory of the University Politehnica of
                       Bucharest. In the laboratory in Bulgaria, hexane: acetone in a ratio of 1:1 v/v was used in
                       the microwave. Sulfur was removed with activated copper. The extraction was followed
                       by purification, which was performed on the florisil segment when using organochlorine
                       pesticides (OCP); polychlorinated biphenyls (PCB) were utilized in the silica/alumina
                       segment for polyaromatic hydrocarbons (PAH). The concentration of components was
                       achieved using the Kuderna-Denish concentrator in Romania, a rotary evaporator with
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
Water 2023, 15, 1012                                                                                          6 of 22

                       nitrogen flow. In Bulgaria, using a silica gel structure, the concentration was achieved in a
                       turbo-evaporator with nitrogen flow.
                            Persistent organic pollutants were analyzed by gas chromatography (GC). In Romania,
                       the electron capture detection method (GC-ECD) was used for OCPs and PCB, and the gas
                       chromatography–mass spectrometry (GC-MS) method was used for PAH.

                       Content of Heavy Metal (HM)
                             Sediments with finer organic content tend to accumulate higher concentrations of
                       HM than coarse sediments. The accumulation of fine and polluting particles is facilitated
                       in deep marine areas, whereas coarse-grained particles dominate in coastal zones. The
                       spatial distribution of HM concentrations in sediments revealed an increasing gradient
                       for some elements in the western part of the Black Sea, with the exceptions of Pb and
                       Ni. The chapter, dedicated to the obtained results, presents a comparison between the
                       values recorded for HM in 2014 with those from 2020. The strong correlation between these
                       elements, particularly for Cu, Cr, and Al, confirms the influence of the mineralogical and
                       granulometric properties of the sediments.
                             Except for Ni, the concentrations of Cd, Pb, Ni, and Cr measured in the sediments of
                       the Romanian coast were below the sediment quality standards. Higher concentrations
                       were found near the Danube delta and the ports of Constanta and Mangalia. HM concen-
                       trations are low in the central and southern tourist areas. Based on the last report of BSC,
                       in Georgia, the average concentration of Fe decreases by 7.5–4% in the south but remains
                       constant in the rest of the country, at 14.5–8.3%. The Mn is evenly distributed at 0.25–0.35%
                       values. The Chorokhi River brings in sediments polluted with mining minerals, causing
                       an accumulation of Cu, Zn, Ni, Cr, and As near Batumi and Gonio. There are no regula-
                       tions in Ukraine for bottom sediments. The estimates were developed using EU-funded
                       programs. In 2017, for Georgia, the highest concentrations were found: Zn—10 µg/g, and
                       Cr—78 µg/g.
                             In 2017, the absolute concentrations of heavy metals decreased in the following order:
                       Zn > Cr > Cu > Ni > Pb > Co > As > Cd > Hg; for 2020, there was the following order:
                       Zn > Cr > Cu > Ar > Ni > Co > Pb > Cd > Hg. Any value measured in 2020 for Cd and Zn
                       exceeded the allowed values of 1.2 µg/g for Cd and 150 µg/g for Zn. The percentage of
                       samples with concentrations higher than the accepted thresholds ranged from 6% for Pb
                       and Hg to 16% for Cr, 56% for Cu, and 90% for Ni. Compared with the 2015 measurements,
                       the Ni level frequently exceeds the value of 20.9 µg/g. The BSC admits that the natural
                       level of Ni in Black Sea sediments is higher than the values admitted for other seas.

                       2.2. Sources of Seawater Pollution
                            The Black Sea receives freshwater from main rivers such as the Danube, Dnieper, and
                       Dniester from the northwestern area. Because 87% of seawater is anoxic, it is vulnerable to
                       anthropogenic impacts, due to its large catchment area and limited connections to other
                       seas. Each year, roughly one-third of the continental runoff freshwater, about 350 km3 /year,
                       flows into the Black Sea. The changes in its ecosystem clearly show it is vulnerable to
                       anthropogenic effects. Some issues must be studied:
                       -    Biodiversity losses due to pollution, invasive species, and habitat destruction;
                       -    Pollution from land and discharged wastewater;
                       -    Overexploitation of marine resources, with a direct impact in the extinction of some
                            fish species or with a massive decrease of their stocks. Overfishing, coastal industrial
                            and tourist development, and heavy maritime traffic have all contributed to the marine
                            resources decline.
                            The main causes of the Black Sea pollution are derived from the land, or are brought
                       about by rivers, air or sediment pollution, and waste discharge. Based on an interna-
                       tional program ongoing since 2002 in the Black Sea, 37 monitoring boats are present, with
                       11 permanently active in five-day cycles, and the rest participating in seasonal programs of
                       monitoring and measurements. Water parameters are monitored for depths up to 1000 m;
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
Water 2023, 15, 1012                                                                                          7 of 22

                       some can explore even up to 1500 m. Based on the measurements from 2020, the Results
                       illustrate some of the principal causes of seawater pollution. Until now, researchers have
                       not considered the effects of war; these will be estimated in time.

                       2.2.1. Nutritive Loads
                            Agriculture is the primary source of nutrients that reach the seawater. The Danube
                       provides about 50% of nutrients in the Black Sea; the rest is supplied by the Ukrainian
                       rivers Dnieper, Dniester, and Bug, the Turkish rivers, atmospheric nitrogen, and municipal
                       and industrial discharges. In recent decades, EU member countries have implemented
                       a new policy of reducing the quantities of fertilizer from agriculture, determined by the
                       nitrogen/phosphorus (N/P) ratios. Unfortunately, due to the widespread use of fertilizers
                       in Ukraine and Russia, the western coastal waters remain high in dissolved inorganic and
                       organic nitrogen, without any improvement. DIN (internationally recognized standard)
                       mentioned that P-PO4 concentrations, on the other Black Sea coasts (S, NE, and N), are
                       approximately three to four times lower than on the western coast. Nutrient inputs from
                       sediments can contribute to progressive eutrophication. In the Results chapter, the nutrients
                       discharged, based on the measurements from 2020, will be mentioned, with their effects on
                       eutrophication. In 2019, 453 monitoring stations were installed in the Black Sea, with the
                       majority in the western part.
                            The phosphate concentration in water reveals the role of phosphorus in the increased
                       biological activity during the warm season. The phosphorus concentration is average at
                       depths of 10–40 m; below, up to 50 m, it decreases, regardless of the season. Silicates are
                       horizontally distributed. Their present average concentrations are lower than reported in
                       the 1960s. Nitrate concentrations are lower than the 1990s average, but with high variability
                       in the northwest region, due to the river input. Compared with other inorganic components,
                       the nitrites have small spatial and seasonal variations. The trends from 2009 to 2019 showed
                       an average increase, followed by a steady decrease until 2020. Ammonium levels are the
                       highest in spring, and decrease when the flow rates of rivers increase, as well as during
                       algal blooms. Except for phosphates, the nutrient concentrations in the Black Sea surface
                       waters decreased between 2014 and 2020.

                       2.2.2. The Hydrological Balance in Seawater
                             The primary element affecting seawater quality is the hydrological balance. Annual
                       and seasonal fluctuations of the water balance determine its physical–chemical characteris-
                       tics. Water balance may be expressed as:

                                        ( Q R + Q P + Q M + Q A ) − ( Q E + Q LM + Q LA ) = ∆V/T                 (1)

                       where QR —is the total rivers flow rate, QP —the amount of precipitation, QM —the flow
                       rate that enters into the Black Sea through the Bosphorus Strait from the Sea of Marmara,
                       QA —the flow rate from the Sea of Azov through the Kerchi Strait, QE —the flow rate lost due
                       to the evaporation, QLM —the flow rate lost due to surface currents in the Seas of Marmara
                       and Azov, and ∆V—changes in sea volume in time T (year or season). Equation (1) may be
                       condensed to:
                                                          F + Q B + QK = ∆V/T                                    (2)
                            Here, F = Q R + Q P − Q E represents the freshwater balance, QB = QM − QLM is the
                       resultant water flow through the Bosporus Strait and QK = QA − QLA is the result of the
                       water flow through the Kerch Strait.
                            The precision of measurements affects the accuracy of the water volume estimation.
                       211 rivers flow into the Black Sea directly or via lagoons, according to the BSC Report.
                       Geographically speaking, the flow rate of rivers from Romania, Crimea, Caucasus, Turkey,
                       and Bulgaria represents the majority of tributary flow from rivers. A total of 58.5% of
                       the Black Sea tributary flows arrive from the Danube, Dniester, and other rivers from the
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
Water 2023, 15, 1012                                                                                           8 of 22

                       northwest. According to the previous measurements, it was observed that the average
                       annual flow rate varies between 287–480 km3 /year.
                             Unfortunately, there is no information on the river flow rates from Georgia and Turkey.
                       The error in estimating the annual average of the tributary flow rates of rivers in the Black
                       Sea is between 9.5–10% and about 3035 km3 /year. The information about the tributary
                       flow rates from Turkey and Caucasus, estimated as 355.6 km3 /year, was received only for
                       2017–2019. The average annual water consumption is 29.6–39.6 km3 /year or 8–11% of the
                       average long-term runoff.
                             An important factor in the hydrological balance of the Black Sea is represented by
                       atmospheric precipitation. Its volume is comparable to the tributary flows from the rivers.
                       The results are obtained by measurements of seasonal and multi-annual precipitation,
                       taken at coastal stations and in the open Black Sea. The minimum precipitation in the
                       open sea area is in summer, when convective precipitation prevails, and the maximum
                       is in autumn and at the beginning of winter, due to the increase of cyclonic activity and
                       the intensification of the vertical convective air currents. The measurements show that
                       regardless of the season, the southern part, the Anatolian coast, and the Caucasus region
                       receive most of the precipitation. The average annual precipitation varies between 119 and
                       662 km3 /year.
                             The hydrological balance must consider also the evaporation of the water. It is influ-
                       enced by air humidity and water vapor pressure as a function of temperature, salinity, and
                       wind speed. The total amount of evaporation was calculated by adding the losses from
                       different locations. Unfortunately, there are not many stations for measuring wind speed,
                       water temperature, surface water salinity, air temperature, and humidity in the north and
                       east part of the Black Sea. The measurements recorded in 2020 show that the evaporation
                       varies between 232 and 441 km3 /year. The NW and NE regions of the Black Sea have the
                       highest rates of evaporation.
                             As a result, river discharges and the amount of precipitation minus evaporation
                       are mainly used to determine the water balance. From 2007, researchers observed the
                       effects of climate change in the Black sea area. The balance of freshwater decreased by
                       67 km3 /year, mainly due to a lack of precipitation. With little precipitation, the average
                       annual evaporation rate increased in 2020 to 417 km3 /year, varying by 38 km3 /year
                       compared with the previously recorded annual average rate.

                       2.2.3. Effects of Port Operations and Municipal Sewage Treatment Plants
                       Maritime Transport
                            The Black Sea has recorded a steady increase in maritime transport over the last ten
                       years. The increased number and dimensions of ships produce increased pollution and
                       perturb the environment. Figure 2a illustrates the travels through the Bosphorus Strait to
                       the Mediterranean Sea in July 2017. Figure 2b,c illustrate, by comparison, the situation in
                       the western part of the Black Sea, of the fishing and transport vessels in July 2018 and 2021.
                       In 2021, they almost doubled. The meaning of the colors in each image is mentioned.
                            Starting in May 2022, the Romanian ports of Constanta, Mangalia, and Sulina have
                       been over-congested. This is due to the war and the increased necessity of transporting
                       cereals from Ukraine to the rest of Europe. After the bombing of the ports of Odessa and
                       Mikolayv, the number of ships from Ukraine drastically decreased. Instead, the Kerch Strait
                       was occupied by ships traveling from Russia to Turkey. Despite being in the most dangerous
                       area of the Black Sea, last year, from Ukraine to Romania and Bulgaria, authorities recorded
                       about 25,000 ship calls. The ecosystem and environment of the Black Sea are undoubtedly
                       impacted by this intense maritime transport.
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
x FOR PEER REVIEW
Water 2023, 15, 1012                                                                                                                                9 9of
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                                                                                                                                                           22

         (a)                                       (b)                                                                   (c)
                                Figure
                                Figure 2.
                                       2. The
                                          The situation
                                              situation of
                                                        of maritime
                                                           maritime transport
                                                                    transport in
                                                                              in the
                                                                                 the Black
                                                                                     Black Sea:
                                                                                           Sea: (a)
                                                                                                (a) 2017;
                                                                                                    2017; (b)
                                                                                                          (b) 2018;
                                                                                                              2018; (c)
                                                                                                                    (c) 2021.
                                                                                                                        2021.

                                      Starting
                                Municipal          in May
                                               Sewage         2022, thePlants
                                                           Treatment        Romanian ports of Constanta, Mangalia, and Sulina have
                                been The
                                       over-congested.         This  is   due
                                             wastewater released by municipal      to the warsewageand thetreatment
                                                                                                              increasedfacilities,
                                                                                                                           necessityindustrial
                                                                                                                                          of transporting
                                                                                                                                                       activi-
                                cereals   from Ukraine
                                ties, shipyards,              to the rest of
                                                      and commercial                Europe.
                                                                                ports           After the
                                                                                         represents          bombing
                                                                                                        another   factor ofcontributing
                                                                                                                             the ports of Odessa          and
                                                                                                                                                to seawater
                                Mikolayv,
                                pollution. the       number of ships(HCB),
                                               Hexachlorobenzene                from Ukraine
                                                                                           lindane drastically     decreased.aldrin,
                                                                                                      (HCH), heptachlor,             Instead,     the Kerch
                                                                                                                                             dieldrin,    and
                                Strait  was    occupied     by   ships    traveling       from    Russia   to  Turkey.
                                polychlorinated (PCB) 28, PCB 52, and PCB 101 are the chemical compounds found in        Despite       being    in  the  most
                                dangerous
                                wastewater.area       of the Black Sea,
                                                 Concentrations        of theselast contaminants
                                                                                      year, from Ukraine        to Romania
                                                                                                        frequently    exceed and        Bulgaria,
                                                                                                                                 the limits     of a author-
                                                                                                                                                      healthy
                                ities recordedMeasurements
                                ecosystem.          about 25,000 ship         calls. The ecosystem
                                                                        in seawater          must be made  and environment
                                                                                                                  at three different of the depths:
                                                                                                                                             Black Sea0are  m,
                                undoubtedly
                                5 m, and 20 m.     impacted      by thisstarting
                                                       In Romania,          intense with maritime2018,transport.
                                                                                                        the total amount of hydrocarbons was
                                82–503 mg/L, values accepted by the BSC against pollution. This is a consequence of the
                                Municipal
                                rehabilitation Sewage
                                                    of twoTreatment
                                                              major sewage Plants stations. Some other chlorinated pesticides, such as
                                heptachlor,     cyclodiene      pesticides
                                      The wastewater released by municipal        (aldrin, dieldrin,
                                                                                                  sewageendrin),    andfacilities,
                                                                                                            treatment      the HCHindustrial
                                                                                                                                          groups were,      in
                                                                                                                                                       activi-
                                Romania,
                                ties,         underand
                                      shipyards,        the commercial
                                                             recommended       ports  values.    The concentrations
                                                                                         represents     another factorfor       HCH = 0.0–7.18
                                                                                                                            contributing                ng/L,
                                                                                                                                               to seawater
                                the cyclodiene
                                pollution.           group 0–2.4 ng/L,
                                               Hexachlorobenzene             (HCB), and heptachlor
                                                                                          lindane (HCH), 0.0–6.07   ng/L varied
                                                                                                                heptachlor,             in the
                                                                                                                                  aldrin,        northwest
                                                                                                                                             dieldrin,    and
                                part of the Black(PCB)
                                polychlorinated          Sea in28,2019.
                                                                     PCBThese  52, and values
                                                                                            PCBare 101lower
                                                                                                        are thethan  those recorded
                                                                                                                  chemical       compounds   in 2009–2012,
                                                                                                                                                   found in
                                before the rehabilitation
                                wastewater.       Concentrations  of theofsewagethese stations.
                                                                                          contaminantsThe previously
                                                                                                              frequentlyrecorded
                                                                                                                              exceed values        were,offor
                                                                                                                                          the limits         a
                                the  cyclodiene      group,    0.0–63.95     ng/L,      for  heptachlor,     0.0–63
                                healthy ecosystem. Measurements in seawater must be made at three different depths: 0ng/L,     and    for  HCH     (lindane),
                                0.0–129
                                m,  5 m, ng/L.
                                           and 20 m. In Romania, starting with 2018, the total amount of hydrocarbons was
                                82–503 mg/L, values accepted by the BSC against pollution. This is a consequence of the
                                2.2.4. Oil Pollution
                                rehabilitation of two major sewage stations. Some other chlorinated pesticides, such as
                                       The ongoing
                                heptachlor,              growth
                                                cyclodiene         in oil and(aldrin,
                                                                pesticides           gas production
                                                                                             dieldrin, around
                                                                                                         endrin),theand Caspian
                                                                                                                          the HCH    Seagroups
                                                                                                                                          has determined
                                                                                                                                                     were, in
                                increased     oil  transportation       in  the     Black    Sea.  When
                                Romania, under the recommended values. The concentrations for HCH = 0.0–7.18the war   is finished,      this  trend would
                                                                                                                                                        ng/L,
                                probably
                                the          increase
                                     cyclodiene          again.
                                                     group        Oil ng/L,
                                                               0–2.4   pollution   andoccurs       when0.0–6.07
                                                                                          heptachlor      crude oilng/L
                                                                                                                      and varied
                                                                                                                             petroleum       products
                                                                                                                                        in the   northwestleak
                                from   tankers,     offshore    platforms,        drilling    rigs, wells,   and  pipelines
                                part of the Black Sea in 2019. These values are lower than those recorded in 2009–2012,         or  when     ships    such  as
                                ferries,  tourist,    military,   or  fishing        ships   discharge    bunker    fuel,
                                before the rehabilitation of the sewage stations. The previously recorded values were, for  waste      oil, or  bilge  water.
                                In these cases, the spills are mostly concentrated near the major ports or along the major
                                the cyclodiene group, 0.0–63.95 ng/L, for heptachlor, 0.0–63 ng/L, and for HCH (lindane),
                                shipping routes.
                                0.0–129 ng/L.
                                       The worst oil pollution occurs when there are accidents with oil tankers, as was the
                                case in 2005 and 2009, with two Turkish ships were damaged and partially sunk in their
                                2.2.4. Oil Pollution
                                territorial waters. Unfortunately, in such accidents, the effects are felt across large surfaces
                                      The ongoing
                                and often     for a quite growth    in oil and
                                                             long period.          Thegas    production
                                                                                         ability              around the
                                                                                                   to track accidents     in Caspian
                                                                                                                              real timeSea  has has    deter-
                                                                                                                                                  increased,
                                mined
                                due to the information received from satellites and drones. Between 2014 and 2016, oiltrend
                                         increased      oil transportation           in the   Black   Sea.  When    the  war     is finished,     this  spills
                                would    probably
                                were visible           increase
                                                  in about     50%again.
                                                                     of theOil       pollution
                                                                                 radar    images,  occurs
                                                                                                      and when     crudetooil
                                                                                                            from 2017             andthey
                                                                                                                              2020,     petroleum       prod-
                                                                                                                                              were visible
                                ucts
                                in 64%leakoffrom
                                              cases.tankers,
                                                       Nowadays,offshore theplatforms,
                                                                                Black Seadrilling
                                                                                                surfacerigs,   wells, and pipelines
                                                                                                         is permanently                     or when
                                                                                                                                air-monitored,          ships
                                                                                                                                                      mainly
                                such   as  ferries,  tourist,   military,    2 or   fishing    ships  discharge    bunker
                                due to the war. About 800 km surrounding the significant seeps is estimated as being           fuel,   waste    oil, or  bilge
                                water.
                                completely exposed to the oil contamination. The effect of this poses a serious threat to the
                                         In  these   cases,   the  spills    are    mostly     concentrated     near   the  major      ports   or  along   the
                                major   shippingOil
                                environment.          routes.
                                                         spills can travel up to 40–80 km when the wind blows. They endanger
                                marineTheresources,
                                             worst oil contaminating
                                                          pollution occurs       thewhen
                                                                                       waterthere     are beaches,
                                                                                                and the   accidentsand  withcan oillast
                                                                                                                                     tankers,    as was the
                                                                                                                                         for months.
                                case in 2005 and 2009, with two Turkish ships were damaged and partially sunk in their
                                territorial waters. Unfortunately, in such accidents, the effects are felt across large surfaces
                                and often for a quite long period. The ability to track accidents in real time has increased,
Environmental Conditions and the Fish Stocks Situation in the Black Sea, between Climate Change, War, and Pollution
Water 2023, 15, 1012                                                                                             10 of 22

                       2.3. Current Situation of Fish Stocks in the Black Sea
                             The International Day of Action for the Black Sea is celebrated annually on 31 October.
                       On this occasion, some actions are required for the entire area, including beach cleaning,
                       and measurements concerning the air, water, and sediment quality. New major goals are set
                       for better conditions for the locals, environment, and biosphere. Last year, the meeting was
                       postponed until 2023 because of the war. The most recent scheduled objectives were related
                       to measures aiming to reduce eutrophication, restore fish reproduction areas, improve
                       compliance with fish catches, and survey invasive species.
                             The last international expedition was conducted in 2020, by an international team of
                       scientists from Romania, Bulgaria, and Turkey, in the western part of the Black Sea.
                             As a member of the research team, we also collected 21 biological samples. The Black
                       Sea sprat prefers colder waters and migrates irregularly. The variations in temperature
                       produced by global warming have affected its population. Due to the war and heavy
                       maritime traffic, it could not migrate in 2022 to the northeastern region, its preferred
                       spawning area. A significant reduction in the migration distance was noticed via satellite
                       monitoring. The Mediterranean Sea and the Black Sea host a large population of whiting,
                       a gregarious and demersal species. In spring, when the temperature reaches 7–8 ◦ C, it
                       approaches the shore, helped by the cold currents. When the water is 10–15 ◦ C in summer,
                       it prefers deep waters. Unfortunately, the whiting population suffered significantly in 2022
                       due to the heavy maritime traffic. In all areas of the Black Sea, the mullet can be found in
                       coastal waters, at depths of 30–100 m, in areas with stony, sandy, or muddy bottoms. The
                       war had a small impact on his development.
                             In the Black Sea, there are 198 species of fish, either native, invasive, or newly intro-
                       duced. To analyze their dynamics, the next indicators were considered: catches, population
                       structure, length and size at maturity, age, class structure, sex ratio, fecundity rates, survival
                       or mortality rates, reproductive stocks, and genetic structure [22,23]. The most common
                       species found in the Black Sea are next illustrated.
                             Pontic shad can be found in open sea and coastal areas, up to depths of 100 m. One of the
                       most significant fish families in the world is the Clupeidae. The largest catches are reported
                       in Sozopol, Cape Emin, and Varna. The Fauna Habitats Directive lists the most well-known
                       anadromous fish species that are at being in danger of extinction. Alosa species are extremely
                       vulnerable to anthropogenic changes, especially related to the access and quality of their
                       breeding areas. Industrial and domestic pollution, water acidification, drainage, land use
                       changes, river barriers, overfishing, the introduction of new species, and, recently, the
                       conflict in the Crimean region are threats to these species. Overfishing during the migration
                       period still remains the main threat. Based on the last BSC report from 2021, less than
                       1400 km2 comprises the space of the breeding areas. A preponderance of groups measuring
                       13.5–14 cm was observed, starting in 2014. It means that the majority are still young and
                       sexually immature. This criterion estimates their status to be “unfavorable–unsatisfactory”.
                             The pelagic fish Engraulis encasicolus ponticus and Engraulis encasicolus maeoticus are
                       the two most well-known anchovy species from the Black Sea. The migration of anchovies
                       from the Mediterranean Sea through the Bosphorus Strait aids in maintaining differences
                       between them. The Black Sea anchovy is longer and has a lower percentage of body fat.
                       Less than 3% of the Black Sea’s anchovy population reaches the sexual maturity of one year,
                       which is the age at which they begin to spawn. A steady annual harvest rate of roughly
                       60% of the total anchovy biomass is noted. In the last five years, fifteen scientific studies
                       have been done to study their behavior, spawning grounds, migration, and wintering.
                             Fortunately, their fish eggs are laid in the southern Black Sea, where they can survive
                       amid ongoing conflict. There is not a well-known annual route for the migration of
                       anchovies. Depending on the velocity of the water currents, water temperature, or the
                       maritime vessels’ routes, this can be modified. Last year, the anchovies’ route changed
                       due to the increased maritime traffic through the Bosphorus. They passed Turkey and
                       traveled directly to Georgia. As a result, Turkey’s anchovy catches were lower than usual.
Water 2023, 15, 1012                                                                                          11 of 22

                       Anchovies 1–3 years old have lengths of 9–13.5 cm. Their dimensional structure and spatial
                       distribution are currently considered to be in a “favorable” state.
                             The sprat, Sprattus sprattus, number in the Black Sea has risen quickly. The sprat
                       biological mass was estimated in 2017 as being 277,720 t. Previously, in 2010 and 2011, the
                       catches were generally low, but starting in 2012, they permanently increased. The length
                       of young fish, of 0–4 years, varies between 4 and 12 cm. The dimensional structure and
                       spatial distribution are currently estimated to be in a “favorable” state.
                             Scad, Trachurus mediterraneus ponticus, is a migratory species found throughout the
                       entire Black Sea. Black horse mackerel is a subspecies of the mackerel from the Mediter-
                       ranean Sea. They migrate in spring, unfortunately, to the conflict zones, for breeding and
                       feeding. In autumn they go to the coasts of Anatolia and the Caucasus. They winter at
                       depths of 20–90 m off the Crimean Peninsula and at 20–60 m in the Caucasus region. Horse
                       mackerels range from 8 to 19 cm, but catches are generally between 12 and 16 cm. It is
                       uniformly distributed in September and October, spending the day 7–12 m deep and 1–3 m
                       above the bottom, and during the night it is located in the middle layer, at 5–10 m deep. Its
                       current situation is considered to be “favorable”.
                             The Black Sea contains a large population of Atlantic Bonito, Sarda sarda, at depths of
                       80–200 m. For its proper living conditions, the water salinity must be 14–39% (g/L), and
                       the temperature must be 12–27 ◦ C. One of the top predators in the Black Sea, tuna fish has
                       a significant economic impact, particularly on Turkish fisheries. The bonito population
                       benefits from the average water temperature increase due to global warming. Compared
                       with the period before 2000, nowadays, the spawning period is longer. It spends more time
                       in the sea than it did before the year 2000, migrating in early spring and feeding on small
                       pelagic fish, such as anchovies, horse mackerel, and sprat. Unfortunately, its number has
                       decreased in the last period, mainly caused by the NW Black Sea pollution, the problems
                       with the migration routes due to the commercial vessels, and intensive fishing from Georgia
                       and Russia. Few mature individuals and almost no fish longer than 50 cm are recorded
                       now in catches. It indicates that adults are not nowadays present in the Black Sea. Between
                       0 and 3 years it grows quickly, but its status is still “unfavorable”.
                             The turbot, Psetta maxima, lives at depths up to 100–140 m, can be found all over the
                       Black Sea, and has a long lifespan. This species has decreased in numbers in the last years,
                       being frequently caught by accident. Only 26 turbot specimens were caught in Bulgarian
                       waters in the 2018 campaign. Their age was 2–7 years, with lengths of 26–70 cm. Its current
                       status is “unfavorable unsatisfactory”.
                             Red mullet, Mullus barbatus, lives near Crimea and Caucasus. There are two types
                       of mullets: migratory and colonized. The migratory mullet crosses the Kerch Strait into
                       the Sea of Azov in spring, for breeding and spawning, and for winter it returns along the
                       Crimean coast. The last year’s war perturbed his migration. The migrant form dominates
                       the catches in Ukraine. The two subspecies, red mullet (Mullus barbatus) and striped mullet
                       (Mullus surmuletus) have recently been the subject of some debates. Finally, these two
                       subspecies were classified together. Generally, it stays at depths of 20–60 m, but its current
                       status is still “unsatisfactory”.
                             Whiting is one of the most prevalent demersal fish in the Black Sea. Without extensive
                       migrations, they spawn in its habitat during the colder months. The young whiting spends
                       about a year in water up to 10 m deep. The adults prefer temperatures between 6 and
                       10 ◦ C, from deep waters of 60–120 m. Fish under six years predominate, representing
                       the commercial concentrations. The whiting is a by-catch, being rarely the target species
                       for fishing. For ages up to 6 years, its length varies between 5.2 and 24.3 cm. Since its
                       assessment is merely indicative, whiting catches cannot be estimated. Its state now is
                       considered to be “favorable”.
                             The thornback ray, Raja clavata, known as the Black Sea Fox, is now in danger of
                       extinction. It lives at the bottom of the sea, at about 300 m deep, but also it may be seen
                       in shallower waters of 10–70 m. Water temperature and pollution are the main factors
Water 2023, 15, 1012                                                                                                                 12 of 22

                                 affecting its distribution. Catches are aged between 1 and 12 years. The adult males are
                                 56–77 cm long and females about 62.3–79 cm. Unfortunately, its condition is still “critical”.
                                      The spotted dogfish, Squalus acanthias, lives throughout the Black Sea, where the
                                 temperatures are 6.5–15 ◦ C. It migrates in autumn to Caucasus, Crimea, and Anatolia,
                                 where there are abundant anchovies and black horse mackerel. It is a viviparous species
                                 that mainly breeds in Ukrainian waters, in the Karkinitsky Bay, Kerch Strait, and Feodosia
                                 Bay. It swims up to the coastal zone at depths of 10–30 m to give birth to the cubs, with an
                                 average of eight per female. The majority of specimens ranging from 1 to 14 years were
                                 7–8 years, and of both sexes. Males and females are 82–88 cm in length at maturity. The
                                 reproductive biomass has significantly decreased in the last decades. Its current condition
                                 is “unsatisfactory”.

                                 3. Results
                                      Starting in 2014, some international expeditions were systematically organized, in
                                 order to monitor environmental parameters, water quality, and biological mass. In 2020,
                                 the last expedition was organized in the western part of the Black Sea, with researchers
                                 from Romania, Bulgaria, and Turkey. Being part of this expedition, I could observe the
                                 methods of collecting physical, chemical, and biological samples. There were observed the
                                 medium-term effects of water pollution and the introduction of invasive species of jellyfish
                                 and aquatic plants. In the following, some results obtained from these measurements will
                                 be presented, and are also compared to the previous years of monitoring.

                                 3.1. Air Monitoring and Air Pollution
                                      The results obtained from the monitoring of the Romanian coast are mainly presented.
                                 Where I have the opportunity, I present also the results of measurements, or the data
                                 reported by other riparian states from this interval. Figure 3 illustrates such measurements
                                 for some environmental parameters. Such an example is illustrated, for March 2020, for the
                                 Romanian seashore, the wind direction, daily temperatures, and average precipitation. In
                                 Figure 3b, the maximum, minimum and average values of temperatures T (◦ C) are marked
                                 in red, and the relative humidity (RH) (%) is in blue. In Figure 3c, the values of the fallen
                                 precipitation (L/m2 ) and the amount of water lost through evaporation are represented.
                                 The remaining positive value of water, which will be accumulated in the sea, is marked
                                 in blue, and the one lost through evaporation is marked in gray. There are days when the
Water 2023, 15, x FOR PEER REVIEW                                                                                      13 of 24
                                 entire amount of water falling (from dew, condensation, waves) is lost through evaporation,
                                 and this appears only in the columns marked with gray.

                           (a)                                            (b)                                     (c)
                                 Figure 3.
                                 Figure 3. Air
                                           Air parameters
                                               parameters for
                                                          for March
                                                              March 2020:
                                                                    2020: (a)
                                                                          (a) Wind direction; (b)
                                                                              Wind direction; (b) Air
                                                                                                  Air temperature;
                                                                                                      temperature; (c)
                                                                                                                   (c) Precipitations.
                                                                                                                       Precipitations.

                                       The
                                       The heavy
                                             heavyMetals
                                                    Metals(HM)(HM)  and
                                                                      andPOP   particles,
                                                                             POP          such
                                                                                   particles,   as Cd,
                                                                                              such    as Pb,
                                                                                                         Cd,Hg,
                                                                                                             Pb, and
                                                                                                                  Hg,benzopyrene-      B(a)P,
                                                                                                                        and benzopyrene‐
                                 were
                                 B(a)P,measured     in the atmosphere
                                         were measured      in the atmospherefrom 2015
                                                                                    fromto2015
                                                                                             2020,
                                                                                                 to based  on emissions
                                                                                                     2020, based            from Romania
                                                                                                                  on emissions     from Ro‐
                                 and
                                 manianeighboring     countries.
                                         and neighboring           They were
                                                               countries.     Theyassociated   with precipitation,
                                                                                    were associated                   wind intensity,
                                                                                                         with precipitation,            and
                                                                                                                                wind inten‐
                                 direction.  The increase
                                 sity, and direction.   Thein   averageintemperature
                                                             increase                     and concentration
                                                                            average temperature                 of atmospheric
                                                                                                       and concentration           reactants
                                                                                                                            of atmospheric
                                 produced     an increaseanofincrease
                                 reactants produced            B(a)P, recorded
                                                                         of B(a)P,inrecorded
                                                                                      the 2020 in
                                                                                                measurements.       Cadmium deposition
                                                                                                    the 2020 measurements.        Cadmium
                                 reached   its peak  in 2017.  Figure    4 illustrates the  recorded    values.
                                 deposition reached its peak in 2017. Figure 4 illustrates the recorded values. Larger    concentrations  of
                                                                                                                                Larger con‐
                                 HM   have   been  discovered    in  the western    part of the Black   Sea. The  first
                                 centrations of HM have been discovered in the western part of the Black Sea. The first figure  presents the
                                 recorded   values for
                                 figure presents    theCd,   Hg, and
                                                         recorded        BaP (µg/g).
                                                                      values    for Cd,For
                                                                                         Hg,Pb,and
                                                                                                theBaPmeasured
                                                                                                          (μg/g).values
                                                                                                                   For Pb,arethe
                                                                                                                              multiplied
                                                                                                                                  measuredby
                                 100, as to
                                 values  arebemultiplied
                                                representedbyon    theassame
                                                                100,      to begraph.   The second
                                                                                 represented    on the graph
                                                                                                         sameshows
                                                                                                               graph.theThevalues  recorded
                                                                                                                              second  graph
                                 shows the values recorded in 2015–2020 as a percentage, compared to 2009, considered to
                                 be the reference year for measurements in the Black Sea. Then, systematic and automatic
                                 measurements began for most of the monitored parameters.
Water 2023, 15, 1012                                                                                                         13 of 22
Water 2023, 15, x FOR PEER REVIEW                                                                                                               14 of 24

                                            in 2015–2020 as a percentage, compared to 2009, considered to be the reference year for
                                            measurements in the Black Sea. Then, systematic and automatic measurements began for
                                            most of the monitored parameters.

                                         (a)                                                              (b)
                                        Figure 4. Air
                                            Figure     deposits
                                                   4. Air depositsfor
                                                                   forHM
                                                                      HM and POPparticles:
                                                                         and POP particles:(a)(a) Values
                                                                                               Values     recorded;
                                                                                                      recorded;       (b) Comparison
                                                                                                                (b) Comparison         with 2009.
                                                                                                                               with 2009.

                                            3.2. Characteristics of the Sediments
                                        3.2. Characteristics of the Sediments
                                                 Table 1 displays the average recorded values of PAHs in the sediment measurements,
                                             Table 1indisplays
                                            realized               the average
                                                         2020, in Romania,       recorded
                                                                             Turkey,         values
                                                                                     Bulgaria,       of PAHs
                                                                                                and Ukraine, forin the sediment
                                                                                                                 three-time         measurements
                                                                                                                             intervals: May,
                                        realized
                                            June, in 2020,
                                                   and  July.inAs
                                                                Romania,    Turkey,
                                                                  part of the         Bulgaria,
                                                                               research           and2 Ukraine,
                                                                                         team, Table   illustratesfor
                                                                                                                   thethree‐time
                                                                                                                       total content intervals:
                                                                                                                                       of the May
                                            11 and
                                        June,  PAHsJuly.
                                                      (µg/kg)   foundofinthe
                                                           As part        sediments  of the
                                                                              research      Romanian
                                                                                         team,   Tablecoast in July 2020.
                                                                                                       2 illustrates  theTable
                                                                                                                           total3content
                                                                                                                                  illustratesof the 11
                                        PAHsa comparison    between
                                                (μg/kg) found         the recordedof
                                                                   in sediments     values  in 2014 andcoast
                                                                                      the Romanian      2020, in
                                                                                                              inorder  to see the
                                                                                                                  July 2020.      appeared
                                                                                                                               Table   3 illustrates a
                                            modifications. The strong correlation between Cu, Cr, and Al confirms their influence on
                                        comparison between the recorded values in 2014 and 2020, in order to see the appeared
                                            the mineralogical and granulometric properties of the sediments.
                                        modifications. The strong correlation between Cu, Cr, and Al confirms their influence on
                                        the Table
                                            mineralogical     and granulometric
                                                  1. Average recorded                properties
                                                                      values of PAHs in 2020.   of the sediments.

                        Romania                              Turkey                          Bulgaria                     Ukraine
                                PAH        PAH                 PAH       PAH                    PAH     PAH                 PAH      PAH
              Sample                               Sample                           Sample                      Sample
                               [g/kg]       [%]               [g/kg]      [%]                  [g/kg]    [%]               [g/kg]     [%]
            Constanta          2230          7        1         810       46          1         974      6            1     340       45
            Costinesti          321          3        2        1093       47          2         221       3           2      423      46
              Eforie           1593         11        3        1078       46          3        2022      7            3     579       49
             Mamaia             563          7        4        790        41          4         341       5           4     1001      39
            Mangalia           2038         19        5        352        38          5         207       7           5     884       43
             Portita            782         23        6        464        40          6        1654      15           6      940      44
             Sulina            2891         32        7        341        40          7         394      32           7     763       42
           Vama Veche          3045         24        8        558        43          8        2298      11           8     712       40

                                            3.3. Seawater Pollution, Characteristics, Nutrients, and Eutrophication
                                                 The samples from the depth were collected in 5 L Teflon Niskin bottles, attached
                                            to a Rosette System equipped with in situ fluorometer. We observed the distance from
                                            the surface, temperature, salinity, fluorescence, and the presence of deep-sea chlorophyll,
                                            as well as at 1 m above the depth of sample collection. In 2020, several monitoring
                                            campaigns were carried out. Three of them targeted the western Black Sea. Table 4 lists
                                            the principal sources of water pollution in all riparian countries based on previous and
                                            2020 measurements. Regarding the content of nutrients that reach the water, agriculture is
                                            the principal source. As I presented in Section 2.2.1, unfortunately, the Danube provides
                                            approximately 50% of the nutrient content, the rest being supplied by the rest of the
                                            rivers, and by urban and industrial discharges. Although measures have been taken to
                                            reduce nitrates and phosphates in agriculture, Ukraine and Russia still maintain high
Water 2023, 15, 1012                                                                                                                    14 of 22

                              concentrations, reflected in the seawater content. Table 5 illustrates the intakes of nutrients
                              discharged into seawater by all riparian countries, where P-PO4—phosphate, TP—total
                              phosphorus, and TN—total nitrates, N-NO3, or total nitrites, N-NO2 .

                              Table 2. Dangerous organic contaminants recorded in the Romanian sediments.

                                     Compound                  Number Samples                 Min [µg/kg]                 Max [µg/kg]
                                   Naphthalene                         61                          1.2                         634.7
                                  Acenaphthylene                       54                          0.8                          78.9
                                     Fluorene                          61                          1.6                          976
                                   Acenaphthene                        54                          2.2                         292.2
                                   Phenanthrene                        58                          4.8                         409.7
                                    Anthracene                         60                          0.3                         294.5
                                   Fluoranthene                        56                           1                          272.8
                                      Pyrene                           58                           1                          325.8
                                Benzo(a)anthracene                     52                          0.4                         279.8
                                     Chrysene                          56                          0.2                          85.8
                                Fluorane(b)benzo(b)                    56                          0.1                         255.1

                              Table 3. Variation of the HM concentrations in sediments.

                                    Heavy Metal                               2014                                     2020
                                       (µg/g)               Samples           Min          Max           Samples       Min             Max
                                          Cu                    14            13.76       50.31            18           8.81           55.07
                                          Cd                    14            0.057       0.386            21          0.024            0.61
                                          Pb                    14            9.21         45.18           20           5.37           57.74
                                          Ni                    14             15.7        57.8            19           9.23           70.42
                                          Cr                    16            7.67        97.88            19            38             88.1
                                          Zn                    19            26.1          85.6           15           28.2           123.1
                                          Mn                    24             349        1425.3           17           257            1637
                                          V                     22             5.3         91.2            21           7.2            55.14
                                          Co                    21            4.37         12.82           19           0.43           14.28
                                          As                    21             8.3          9.5            20           9.7             14.3
                                          Hg                    24             2.8         3.29            19          3.42             5.88

                              Table 4. Principal sources of the seawater pollution.

                                                       Sources of Pollution
                               Stationary
                                                   Run-Offs from            Coastal Diffuse          Air and            Ships and Marine
             Types            Land-Based
                                                     Rivers 2                 Sources 3            Sediments 4             Platforms 5
                               Outfalls 1
          Chemicals:                +                                                +                                            +
      Persistent organic            +                      +                         +                    +                       +
      Oil and petroleum             +                      +                         +                    +                       +
           Nutrients                +                      +                         +                    +                       +
       Trace elements               +                      +                         +                    +                       +
         Radioactive                                       +                                              +
         Marine litter              +                      +                         +                                            +
           Biologic                 +                      +                         +                    +                       +
           Microbial                +                      +                         +                                            +
     Exotic species of fish         +                      +                         +                                            +
                              Note(s): 1 Liquid industrial waste, oil spills, insufficiently treated sewage from coastal cities and settlements;
                              2 Nutritive inputs from agriculture, industry, mining, and municipal sewage; 3 Inputs of organic materials from

                              agriculture, animal husbandry, and unmanaged tourism, mainly through land runoff (coastal rainwater and
                              groundwater); 4 Air pollution as smoke, dust, and exhaust gases, regardless of the place of origin; 5 Discharge
                              of solid waste, from explosions and dredged materials, lost fishing nets, or from the introduction of foreign
                              marine organisms.
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