Sensors and biosensors for monitoring marine contaminants

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Trends in Environmental Analytical Chemistry xxx (2015) xxx–xxx

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Review

Sensors and biosensors for monitoring marine contaminants Celine I.L. Justino a,b, * , Ana C. Freitas a,b , Armando C. Duarte a , Teresa A.P.Rocha Santos a a b

Department of Chemistry & CESAM, University of Aveiro, Campus de Santiago, Aveiro 3810-193, Portugal ISEIT/Viseu, Instituto Piaget, Estrada do Alto do Gaio, Galifonge, Lordosa 3515-776, Viseu, Portugal

A R T I C L E I N F O

A B S T R A C T

Article history: Received 30 December 2014 Received in revised form 23 February 2015 Accepted 24 February 2015

The marine environment plays an important role in the global climate regulation, mainly as a major source of biodiversity. However, the climate change and the human activity impacts have increasingly disrupted the natural balance in marine environment. The European Union, through the commitment undertaken in 2008 by the Marine Strategy Framework Directive (MSFD) determined to take until 2020 every necessary step to achieve a healthy marine environment. Thus, the continuous monitoring of contaminants at low concentrations is of great importance for the environmental protection. In this field, the marine sensors and biosensors have been identified as potentially important analytical devices using technological developments such as miniaturized electronics, small scale networks, and wireless communication in order to produce advanced analytical tools for the continuous monitoring of the ‘good environmental status’ of the marine environment. This overview provides a state of the art of sensors and biosensors for monitoring contaminants in marine waters. ã 2015 Elsevier B.V. All rights reserved.

Keywords: Biosensor Contaminants Hazardous priority substances Marine Strategy Framework Directive Marine waters Priority substances Sensor

Contents 1. 2. 3. 4.

5.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Marine Strategy Framework Directive (MSFD) . . . . . . . . . . . . . . . . . . . . . . . . . . . Contaminants of concern for obtaining good environmental status of marine waters Current marine strategies for monitoring contaminants in marine waters . . . . . . . . Analytical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Sensors and biosensors for monitoring marine contaminants . . . . . . . . . . . . . 4.2. Heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.1. Organochlorine compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.2. Polycyclic aromatic hydrocarbons (PAH) . . . . . . . . . . . . . . . . . . . . . . . 4.2.3. Toxins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.4. 4.2.5. Nutrients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pharmaceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.6. Other contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction The marine environment plays an important role in the global climate regulation, being a major source of biodiversity. The

* Corresponding author: Tel.: +351 232 910 100; fax: +351 232 910 183. E-mail address: [email protected] (C.I.L. Justino).

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marine resources can be used to obtain new products and develop new services, presenting potential solutions regarding the challenges that affect our planet, including a sustainable supply of food and energy, new industrial materials and processes, new bioactive compounds, and new health treatments [1]. However, the marine environment is also increasingly vulnerable to climate change, and human activities impacts attendant on industrial, tourist, and urban development [2]. The Integrated Maritime

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Policy was proposed in 2007 in order to enhance the sustainable development of the European maritime economy to the “Europe 2020”, with the following priorities: (a) a smart growth, developing an economy based on knowledge and innovation; (b) a sustainable growth, promoting a more resource efficient, greener, and more competitive economy; and (c) an inclusive growth, fostering a high-employment economy delivering social and territorial cohesion [3,4]. Furthermore, the most important initiative of the European Union was the Marine Strategy Framework Directive (MSFD), undertaken in 2008, where every necessary step to achieve a healthy, protected, and preserved marine environment was agreed to be taken until 2020 [5]. This review paper has the objective of reviewing the state of the art of current sensors and biosensors (2008–2015) over other analytical methodologies used for monitoring the contaminants in the marine waters which are covered by the MSFD, as well as other contaminants with a potential for screening the marine water quality.

ecotoxicological data; (b) levels of pollution effects are below environmental target levels representing harm to the organism, population, community and ecosystem levels; and (c) concentration of contaminants in water, sediment and/or biota, and the occurrence and severity of pollution effects, should not be increasing. In addition, “The Ocean of Tomorrow 2013” [10] referred that the development of competitive and innovative marine technologies is necessary to assess and monitor the good environmental status of the seas, contributing to their sustainable operation. In particular, sensing technologies are necessary to improve reliable measurements of key parameters in the sea, being the biosensors for real time monitoring of biohazard and manmade chemical contaminants in the marine environment and the innovative multifunctional sensors for in situ monitoring of marine environment and related maritime activities, two of the joining research forces to meet challenges in ocean management [10]. Thus, the development of early warning systems such as smallscale sensor technologies is urgently required in order to provide selective and sensitive detection of marine contaminants.

2. The Marine Strategy Framework Directive (MSFD) The objective of the MSFD is to achieve or maintain a good environmental status in the marine environment by the year 2020 at the latest (Art. 1 of MSFD) [5], being the GES defined in the MSFD as the environmental status of marine waters where these provides ecologically diverse and dynamic oceans and seas which are clean, healthy, and productive, allowing the use of the marine environment to a sustainable level, therefore protecting its potential for current and future generations. The definition of GES is based upon 29 criteria and 56 indicators specified for 11 high-level qualitative descriptors by the Commission Decision of 1 September 2010 [6] on criteria and methodological standards on good environmental status of marine waters. For that purpose, the MSFD suggests the development and implementation of marine strategies to the protection and preservation of the marine environment, preventing its deterioration and reducing inputs to phasing out pollution, also ensuring that there are no significant impacts on or risks to marine biodiversity, marine ecosystems, human health or legitimate uses of the sea” (Art. 1(2) of MSFD) [5]. The marine strategies consist in two major tasks, that is, the preparation and the programme of measures. The preparation includes: (a) the analysis of essential features and characteristics (e.g., physical, biological, and chemical features, as well as habitat types and hydro-morphology), analysis of predominant pressures and impacts on the environmental status of marine waters, as well as economic and social analysis of the use of the waters and of the cost of degradation of the marine environment, by each Member State; (b) determination of good environmental status; (c) establishment of environmental targets and associated indicators; and (d) establishment and implementation of monitoring programs. The program of measures consists in the development of measures to achieve or maintain GES. Under the MSFD and in order to assess the achievement of a GES, the concentrations of contaminants must be at levels not giving rise to pollution effects, being the concentration of contaminants in the marine environment (listed as priority substances in Annex X of the Directive 2000/60/EC [7] and further regulated in Directive 2008/105/EC – Annex II [8]) and their effects need to be assessed considering the impacts and threats to the ecosystem [6]. The task group 8 report from the European Commission [9] referred that the combination of new and conventional effect-based methodologies with the assessment of environmental concentrations of contaminants provides a powerful and comprehensive approach and recommended three core elements for data assessment: (a) concentrations of contaminants in water, sediment and/or biota are below environmental target levels identified on the basis of

3. Contaminants of concern for obtaining good environmental status of marine waters According to Law et al. [9], contaminants are defined as substances (i.e., chemical elements or compounds) or groups of substances that are toxic, persistent, and liable to bioaccumulate, and other substances or groups of substances, which give rise to an equivalent level of concern. Furthermore, chemical contaminants are commonly classified as: (a) stable trace elements, such as cadmium, lead, mercury, and tin; (b) organic substances, such as persistent organic pollutants, hormones, veterinary medicines, and pharmaceuticals; (c) hydrocarbon pollution as fuel, crude oil, and oil products; and (d) radionuclides [9]. On the other hand, several factors should be considered in order to monitor the marine environment, such as contaminant nature, sources, distribution, concentration, persistence, uptake into biota, and effect on ecosystem [11]. Thus, the monitoring of contaminants for the protection of the marine environment is the purpose of the Descriptor 8 under the MSFD, also being an urgent concern in marine research. Concerning the contaminants which are hazardous substances, the MSFD (Annex III, Table 2) [6] considered as contamination, the introduction of: (a) synthetic compounds (e.g., priority substances under the Directive 2000/60/EC [7], which are relevant for the marine environment such as pesticides, pharmaceuticals, antifoulants); (b) non-synthetic substances and compounds (e.g., heavy metals and hydrocarbons); and (c) radionuclides. Thus, the Directive 2000/60/EC [7] has included a list of 33 priority substances/groups of priority substances and among them 20 considered as priority hazardous substances (H), which are listed in Table 1. Recently, such list was revised in Report COM(2011) 875 [12] and 15 additional priority substances (among them 6 hazardous priority substances) was included, as also shown in Table 1. It should be referred that in the MSFD, there are no specifications for monitoring frequency, since the cycle of assessment, determination of GES, target setting, monitoring and establishment of measures should be reviewed and updated every six years [13]. However, some indicators should be assessed and monitored with high data acquisition frequency, such as in the case of priority substances with a frequency of one month [13]. 4. Current marine strategies for monitoring contaminants in marine waters There are several strategies and tools employed for the assessment of marine environment, i.e., in sampling, observation

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Table 1 Priority substances/groups of priority substances considered in the Directive 2000/60/EC [7] and in the Report COM(2011) 875 [12]. H – hazardous priority substance. Priority substances/groups of priority substances (Directive 2000/60/EC) Heavy metals and their compounds:

-

cadmium nickel lead mercury (H)

Organotin compounds:

- tributyltin compounds (H); tributyltin-cation

Organochlorine compounds:

- chloroalkanes (C10-C13) (H) - alachlor - brominated diphenyl ether (H); pentabromo diphenil ether (congeners n 28, 47, -

99, 100, 153 and 154) 1,2-dichloroethane dichloromethane

Pesticides:

-

atrazine chlorfenvinphos chlorpyrifos diuron endosulfan (H) isoproturon simazine trifluralin

Alkilphenolic compounds:

- nonylphenol (H); 4-nonylphenol (H); - octylphenol; 4-octylphenol Aliphatic and polycyclic aromatic hydrocarbons:

-

trichloromethane (chloroform)

benzene naphthalene anthracene (H) fluoranthene; polyaromatic hydrocarbons (H); benzo(a) pyrene (H); benzo(b) fluoranthene (H); benzo(g,h,i) perylene (H); benzo(k) fluoranthene (H); indeno(1,2,3-cd) pyrene (H)

di-(2-ethylhexyl) phthalate hexachlorobenzene (H) trichlorobenzene pentachlorobenzene (H) hexachlorobutadiene (H) hexachlorocyclohexane (H) pentachlorophenol

Priority substances (Report COM(2011) 875)

-

aclonifen bifenox cybutryne cypermethrin dichlorvos terbutryn 17a-ethinylestradiol 17b-estradiol

and marine measurements and analysis since data availability and its collection are the major difficulty to marine environment assessment, target setting and trends monitoring [13,14]. Traditionally, samples were collected with ships and analyzed on board or after returning to the laboratory [14]. Several strategies such as platforms and instruments have been developed to perform automated marine measurements [14] such as satellite, submersible, drifter, towed body, remote-operated vehicle, and “SmartBuoy”. These strategies rely on direct sampling, airborne and satellite imagery, hydrological measurements using probes for conductivity, temperature, and depth, remote sensing with the use of electromagnetic waves and acoustic methods [13]. On the other hand, the acquisition, processing, integration and visualization of data obtained using these tools are the steps involved in marine monitoring, importance and integration of which depends on the goals and objectives established as well as on the specific indicators to be monitored [13]. The approaches that could be useful for an effective monitoring of the spatial scale relevant to the MSFD listed by Zampoukas et al. [13] are moorings and buoys, ships, continuous plankton recorder,

-

diclofenac dicofol (H) perfluorooctane sulfonic acid (H) and its derivatives quinoxyfen (H) dioxins and dioxin-like compounds (H) hexabromocyclododecane (H) heptachlor/heptachlor epoxide (H)

underwater video and imagery, underwater acoustics, remote sensing, as well as autonomous underwater vehicles and gliders. However, most of the remote or autonomous measurements carried out are based on sensors to study oceanographic parameters such as temperature, conductivity, depth, and turbidity [15]. 4.1. Analytical techniques One of the main difficulties of the monitoring of marine contaminants is their occurrence at low concentrations, which are sufficient to produce a negative impact on marine ecosystems. Thus, the analytical methodologies should be able to detect and determine such pollutants at ng L
1 or pg L
1 level. For example, the liquid chromatography coupled to tandem mass spectrometry with electrospray ionization in negative mode (LC/ESI-MS/MS) [16] or gas chromatography coupled to tandem mass spectrometry (GC–MS/MS) [17] have been used to determine synthetic steroid estrogens in marine waters. Other analytical techniques such as those combining ultrahigh-pressure LC (UHPLC) with triple-

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quadrupole linear ion-trap MS (UHPLC-QTRAP1MS) [18] allows the identification of polar organic contaminants in marine waters. In addition, Sánchez-Avila et al. [19] proposed the combination of stir bar sorptive extraction with thermal desorption-GC–MS to the determination of 49 organic pollutants (organochlorine pesticides, polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), polybrominated diphenyl ethers, and nonylphenol) in seawater with limits of detection between 0.011 and 2.5 ng L
1), which are lower than the environmental quality standards [8]. Recently, an analytical methodology employing C18 SPE cartridges (for pre-concentration and clean-up) and an ultra-fast LC coupled to fluorescence detector (UFLC-FLD) was proposed to the determination of 4-nonylphenol and 4-octylphenol covered by the MSFD, as well as 17b-estradiol and 17a-ethynylestradiol in marine waters covered by the Report COM(2011) 875, with limits of detection between 2.0 and 23 ng L
1 [20]. The stir bar sorptive extraction with thermal desorption-GC–MS was also used to determine other contaminants not covered by the MSFD, that is, organic booster biocides (Chlorothalonil, Dichlofluanid, Sea-Nine 211, Irgarol 1051, and TCMTB) in seawater [21] with limits of detection of 0.01, 0.03, 0.008, 0.005, and 0.9 mg L
1, respectively. Concerning the presence of antibiotics and other pharmaceuticals in seawater, various analytical techniques such as LC/ESI-MS/MS and UHPLC-MS/MS have been applied to the determination of antibiotics such as sulfadiazine, sulfamethazine, sulfamerazine, sulfamethoxazole, chloramphenicol, lincomycin, and tylosin [22] as well as non-steroidal anti-inflammatory drugs and analgesics [23]. Bayen et al. [22] employed direct injection in LC/ESI-MS/MS to the fast and high-throughput screening of water samples, obtaining limits of detection between 0.16 ng L
1 for tylosin and 26 ng L
1 for lincomycin. Paíga et al. [23] have applied UHPLC-MS/ MS for the simultaneous determination of dipyrone, acetaminophen glucuronide, acetylsalicyclic acid, acetaminophen, carboxyibuprofen, hydroxyibuprofen, p-aminophenol, ketoprofen, naproxen, nimesulide, diclofenac, and ibuprofen in seawater samples, obtaining limits of detection between 0.02 ng L
1 for diclofenac and naproxen and 8.18 ng L
1 for carboxyibuprofen. Other recent techniques could also be applied to the marine waters for the monitoring of physical and chemical variables. For example, Tecon et al. [24] have developed a multistrain bacterial bioreporter platform for the monitoring of hydrocarbon contaminants in marine environments. Mills and Fones [15] reviewed the in situ automatic analyzers, such as flow injection and spectroscopic methods, as an approach to achieve in situ measurements of dissolved gases, nutrients, organic chemicals, and trace metals in marine environment. Recently, Marrucci et al. [25] proposed the use of semi-permeable membrane devices to monitor PAH and PCB in marine protected areas of Western Mediterranean Sea at very low concentrations in the range of pg L
1. However, such analytical techniques required sample preparation and sometimes preconcentration steps in order to carry out the quantitative assessment of trace concentrations of marine contaminants, which could involve long time of analysis, cost and resources, being increasingly higher in the in situ continuous monitoring. Thus, the long time for interpretation of results is not appropriate to rapid alarm systems. 4.2. Sensors and biosensors for monitoring marine contaminants A “chemical sensor” is commonly defined as a device that transforms chemical information, ranging from the concentrations of specific components to the global properties of samples, into an analytically useful signal [26]. In a particular field such as the marine environment, a sensor can be defined as a device that produces a response to a change in a physical condition such as temperature or thermal conductivity, or to a change in chemical

concentration [15]. In sensors and biosensors, the analytical performance is of utmost importance in order to decide about their future applicability in real samples and thus the analytical reliability (sensitivity and selectivity), the analytical capacity (limit of detection), and the analytical variability (repeatability and reproducibility) should be considered for each developed (bio) sensor [27]. The main advantages of sensors and biosensors are the rapid analysis, the simple or unnecessary sample pre-treatment, the in situ analysis, the low volume of samples, the low use of solvents, the low cost of assays, and use as remote devices. According to Albaladejo et al. [2], among the small-scale sensor networks, the wireless sensor networks are attractive solutions to monitor the marine environment since they are easy to deploy, operate and dismantle, and they are relatively inexpensive. Such sensor networks consist of a processor, a radio module, a power supply, and one or more sensors connected between them [2]. Thus, in situ and remote sensing platforms should be developed in order to monitor the marine environment in appropriate scales of time and space. As a multidisciplinary team of researchers is needed from different fields of genomics, chemistry, physics, and nanotechnology, the development of such sensing platforms is highly challenging but also very interesting for the future monitoring of marine environment, also being a hot area in future I&D. Sensors and biosensors can be used for monitoring the marine environment concerning important physical, chemical and biological variables such as temperature, pressure, turbidity, salinity, water speed, dissolved oxygen, hydrocarbons, swell, pH, chlorophyll, rhodamine, blue-green algae phycocyanin, ammonium/ ammonia, as well as nitrate and chloride, as identified by Kröger et al. [28] and Albaladejo et al. [2]. However, this review would highlight the development of sensors and biosensors for the detection and determination of marine pollutants which is of great interest essentially due to the impact of the MSFD until 2020, as already discussed in the Section 2. Table 2 shows the results obtained with existent sensors and biosensors for the monitoring of marine contaminants developed between 2008 and 2015, including their analytical performance and advantages. The two main classes of such analytical platforms are based on electrochemical and optical principles, being the electrochemical sensors and biosensors being the the most used for the monitoring of contaminants in marine waters, as shown in Table 2. The main advantages of such electrochemical sensors and biosensors are generally their portability, field deployability, and easy fabrication, which are important for their incorporation in marine platforms [29,30]. 4.2.1. Heavy metals In the marine environment, the heavy metals are considered important pollutants due to their non-biodegradability; lead and cadmium ions have been considered the most toxic and hazardous [31]. According to the United States Environmental Protection Agency (EPA), the regulated maximum levels of lead and cadmium are about 15 mg L
1 (15 ppb) and 5 mg L
1 (5 ppb), respectively. Güell et al. [31] have developed a sensing device based on screenprinted electrode coupled with square wave anodic stripping voltammetry to the monitoring of lead and cadmium in seawater samples (Table 2). Güell et al. [31] obtained limits of detection in mg L
1, that is, 1.8 mg L
1 for lead and 2.9 mg L
1 for cadmium, also showing a linear analytical response between 10 and 2000 mg L
1 and a stability of 10 days. Such metals were analyzed in spiked seawater samples. Recently, Henríquez et al. [32] have determined cadmium concentrations in natural seawater sample with an automatic multi syringe flow injection system coupled to a flowthough screen-printed electrode sensor (Table 2). Henríquez et al. [32] have obtained a limit of detection of 0.79 mg L
1 with a

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Table 2 Sensors and biosensors for the monitoring of contaminants in the marine waters, developed between 2008 and 2015. (Bio) sensor type

Contaminant

Analytical performance

Advantages

Heavy metals Sensor based on screen-printed electrode coupled with square wave anodic stripping voltammetry

Lead

Linear range: 10– 2000 mg L
1; LOD: 1.8 mg L
1 Linear range: 10– 2000 mg L
1; LOD: 2.9 mg L
1 LOD: 0.79 mg L
1

Stability during at least 10 days; low cost; easy [31] analysis

Cadmium

Multisyringe flow injection system coupled to flow- Cadmium though screen-printed electrode sensor Sensing device based on Nafion glassy-carbon electrodes

Lead Cadmium

Electrochemical sensor based on magnetic nanoparticles of iron oxide functionalized with dimercaptosuccinic acid

Lead

Cadmium Potentiometric chemical sensor

Lead Cadmium

Electrochemical sensor based on screen-printed electrodes

Lead Cadmium

Electrochemical biosensor based on differential pulse voltammetry Optical sensor

Hg2+ (mercuric ion) Hg2+ 2+

Electrochemical sensor based on voltammetry

Hg

Electrochemical sensor based on voltammetry

Copper

Electrochemical sensors based on impedimetry Electrochemical sensors based on screen-printed electrodes Electrochemical sensor based on screen-printed electrodes Electrochemical sensor based on magnetic nanoparticles of iron oxide functionalized with dimercaptosuccinic acid Potentiometric chemical sensor

Copper Zinc

Optical sensor

Organochlorine compounds Electrochemical sensor based on potentiometry Electrochemical sensors based on screen-printed electrodes Polycyclic aromatic hydrocarbons Sensor based on SERS

Toxins Biosensor based on SPR

Silver

Linear range: 0–50 ppb; LOD: <1 ppb Detection range: 10
7– 10
2 M; LOD: <0.4 nM Detection range: 10
7– 10
2 M; LOD: <0.06 nM Detection range: 0– 100 ppb; LOD: 0.31 mg L
1 Detection range: 0– 100 ppb; LOD: 7.0 mg L
1 Linear range: 0–2 mM; LOD: 0.05 mM Detection range: 125– 1250 nM; LOD: 100 nM Detection range: 0.1– 100 nM; LOD: 0.67 nM Detection range: 1–5 mM; LOD: 157 nM Detection range: 0.48– 3.97 mM; LOD: 0.115 mM Linear range: 10–90 ppb; LOD: 13 ppb Detection range: 0– 100 ppb; LOD: 0.53 mg L
1 Linear range: 0–50 ppb; LOD: <1 ppb Detection range: 10
7– 10
2 M; LOD: <0.2 nM Detection range: 10
7– 10
2 M; LOD: <30 nM Detection range: 375– 1250 nM; LOD: 100 nM

Hexachlorocyclohexane Detection range: 10
10– 10
3 M; LOD: 10
10 M 4-chlorophenol Detection range: 0– 25 mM; LOD: 0.43 mM

[32]

[29]

Portability; field-deployability monitoring tool

[30]

Rapid measurements

[33]

Long-term stability; possible integration into automatic control systems

[34]

Simple, cost-effective and rapid method

[35] [36]

Possible regeneration and reusability

[37]

Stability of 72 h

[38] [39] [40]

Long-term stability; possible integration into automatic control systems Portability; Field-deployability monitoring tool

[34]

Rapid measurements

[33]

Rapid method

[36]

[30]

[41] In situ analysis

[40]

Naphthalene Anthracene Anthracene and fluoranthene

LOD: 10 ppb LOD: 310 pM LOD: 0.3 nM

In situ analysis; chemical stability Suitable for incorporation on a mooring Portable sensor

[42] [43] [44]

Saxitoxin

Detection range: 0– 50 ng mL
1; LOD: 0.82 ng mL
1 Detection range: 0– 50 ng mL
1; LOD: 0.36 ng mL
1 Detection range: 0– 50 ng mL
1; LOD: 1.66 ng mL
1

Multiplexed platform; rapid sample preparation; fast results; cost effective; real time results

[45]

Autonomous method

[46]

Okadaic acid

Domoic acid

Nutrients Electrochemical sensor based on amperometry

Detection range: 0– 10 ppb; LOD: 0.5 ppb Detection range: 0– 10 ppb; LOD: 2.5 ppb Linear range: 0–50 ppb; LOD: 0.5 ppb

Good sample throughput (14 h
1); low consumption of sample (1.3 mL); automatic system Portability; field-deployability; long service times

Reference

Phosphate

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Table 2 (Continued) (Bio) sensor type

Contaminant

Electrochemical sensor based on voltammetry

Silicate

Electrochemical sensor based on voltammetry

Silicate

Electrochemical sensor

Nitrate

Pharmaceuticals Biosensor based on SPR

Estradiol

Electrochemical sensor based on voltammetry

Diclofenac

Other contaminants Biosensor based on screen-printed electrodes

Chlorpyrifos

Optical sensor

Thiocyanate

Electrochemical sensors based on screen-printed electrodes

Phenol Catechol

Analytical performance Detection range: 0.10– 5.21 mM; LOD: 0.05 mM Detection range: 0.30– 145 mM; LOD: <1 mM Detection range: 0.50– 134.8 mM; LOD: 0.5 mM Detection range: 10– 200 mM; LOD: 4.5 mM

Detection range: 0.3125– 20.0 ng mL
1; LOD: 0.17 ng mL
1 Detection range: 0.18– 119 mM; LOD: 0.04 mM

Advantages

Reference

Easy and fast detection; sensor easily adaptable [47] on different platforms such as moorings, gliders or floats [48] Good stability; high precision and lifetime Disposable sensors

[49]

No need for labeling; rapid method; possibility [50] for chip regeneration Easy fabrication

Detection range: 0– Portable biosensor 16 mM; LOD: 2 mM Linear range: 4– Compact design; easy operation 400 mg L
1; LOD: 3 mg L
1 Detection range: 0– 5.5 mM; LOD: 0.25 mM Detection range: 0–5 mM; LOD: 0.13 mM

[51]

[52] [53] [40]

LOD: Limit of detection; OFET: organic polymer field effect transistor; SERS: surface-enhanced Raman scattering; SPR: surface plasmon resonance.

cadmium sensor, which also provides a good sample throughput of 14 h
1 and low consumption of reagent and sample (1.3 mL). According to the limit values recommended by EPA for such heavy metals, the sensing devices developed by Güell et al. [31] and Henríquez et al. [32] are viable tools for metal monitoring in seawater. Yantasee et al. [29] have developed a sensing device based on Nafion glassy-carbon electrodes for the simultaneous detection of cadmium and lead in non-pretreated natural waters (Table 2). Limits of detection of 0.5 ppb of lead and 2.5 ppb of cadmium were obtained with the sensor with a minimal amount of preconcentration time of few minutes (3 min) in a very low concentration range (0–10 ppb) and without any sample pretreatment [29]. The same research group [30] also suggested another electrochemical sensor for the detection of lead and cadmium in seawater but by using magnetic nanoparticles of iron oxide functionalized with dimercaptosuccinic acid (Table 2). With this sensor, Yantasee et al. [30] have obtained a limit of detection of 0.5 ppb for lead in a linear response range of 0–50 ppb, and limit of detection lower than 1 ppb for cadmium. Rudnitskaya et al. [33] also proposed sensors for cadmium and lead but applying an array of potentiometric chemical sensors for their detection in a concentration range of 10
7–10
2 M (Table 2). According to Rudnitskaya et al. [33], the developed sensors were able to detect lead down to the 0.4 nM and cadmium down to 0.06 nM, also being able to determine simultaneously such cations in artificial seawater with an accuracy of about 20%. Aragay et al. [34] have also developed a sensing system based on an electrochemical methodology (screen-printed electrodes) for determination of cadmium in seawater samples, as well as lead (Table 2). Aragay et al. [34] obtained detection limits of 7.0 mg L
1 and 0.31 mg L
1 for cadmium and lead, respectively, but the high relative standard deviation for response stability (period of 16 days) for cadmium (33%) and lead (24%) was the major limitation of such sensor. Copper is also considered a water contaminant occurring in seawater through natural processes and man-made activities such as mining and petroleum refining [38]. Various sensors have been developed for the detection of such contaminant in seawater, as

shown in Table 2. For example, Twomey et al. [38] present an electrochemical sensor based on microelectrode arrays to the detection of copper between 1 and 5 mM, obtaining a limit of detection of 157 nM. Herzog et al. [39] also fabricated sensors for detection of copper by stripping voltammetry, for operation in marine environment. According to the results obtained, the sensors operated in concentration range of 0.48–3.97 mM with a limit of detection of 115 nM, which is better than that obtained by Twomey et al. [38]. Regarding mercury, Lai et al. [35] have developed a highly selective electrochemical biosensor based on differential pulse voltammetry for Hg2+, which is the highly toxic ionic form of mercury, in aqueous solution (Table 2). Lai et al. [35] have used the hemin as a redox indicator to generate a readable electrochemical signal; Fig. 1 shows the voltammograms of the biosensor before and after the reaction of Hg2+ with and without hemin (1), as well as the schematic illustration of the mechanism of detection of Hg2+ biosensor using the hemin as a redox indicator (2). Linear correlation between the analytical signal and concentrations of Hg2+ was obtained (R2 = 0.9983) between 0 and 2 mM with a limit of detection of 0.05 mM. However, when applied in real samples (seawater), no signal was obtained for Hg2+, and the standard addition method was applied for the determination of Hg2+ concentration, obtaining good recovery values (96.69–104.46%) [35]. Lai et al. [35] considered that the biosensor was applicable for practical detection of Hg2+. 4.2.2. Organochlorine compounds Anirudhan and Alexander [41] have developed an electrochemical sensor based on potentiometric principles for the determination of hexachlorocyclohexane in various real samples such as seawater, which were spiked with such contaminant (Table 2). The hexachlorocyclohexane is an organochlorine pesticide which was determined in the sensor in the range of 10
10–10
3 M with high selectivity and sensitivity and limit of detection of 10
10 M, which is lower than other method of detection of such contaminant, such as electrochemical assays [41]. According to Tankiewicz et al. [54], the pesticides are among the most dangerous environmental

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Fig. 1. (1) Cyclic voltammograms of the electrochemical biosensor on the sensing interface obtained before (dot line) and after (solid line) reaction with 5 mM Hg2+ for 1 h in 10 mM Tris–HCl buffer (pH 7.4) containing (A) 1 mM hemin and (B) no hemin; (2) schematic illustration for electrochemical detection of Hg2+ using hemin as a redox indicator. Sequence of the DNA probe: 50 -HS-C6-TTTTT (reprinted from Lai et al. [35] with permission from Elsevier).

pollutants because of their stability, mobility, and long-term effects on living organisms. On the other hand, they can undergo transformations that lead to the production of substances of even greater toxicity [54]. Thus, it should be highlighted that rapid and efficient analytical techniques such as sensors should be developed in the near future in order to detect any increase in the degree of contamination of marine waters and living organisms. 4.2.3. Polycyclic aromatic hydrocarbons (PAH) Péron et al. [42] have developed a sensor based on surfaceenhanced Raman scattering (SERS) for the detection of trace concentration of naphthalene in seawater, obtaining a limit of detection of 10 ppb (Table 2). According to Ibañez and Escandar [55], the main problem to determine PAH in natural water samples is the potentially very low concentration levels, which is associated with their low water solubility. However, sensitive sensors are able to successfully determine such contaminants. For example, Kolomijeca et al. [43] have reported the continuous in situ detection of anthracene in seawater with a high sensitive Raman sensor based on SERS, obtaining a limit of detection of 310 pM (Table 2). Recently, the same research group [56] have developed an autonomous in situ Raman sensor also based on SERS for the detection of other PAH in seawater, such as fluoranthene. Kolomijeca et al. [56] have used an integration time of only 10 s

but only qualitative results were reported and based on Raman signals. However, in another work, Kolomijeca et al. [44] applied the portable SERS sensor for monitoring PAH in seawater, such as anthracene and fluoranthene using spiking experiments, and a limit of detection of 0.3 nM was obtained also with an integration time of 10 s (Table 2). 4.2.4. Toxins McNamee et al. [45] have developed a multiplex surface plasmon resonance (SPR) biosensor method for the detection of saxitoxin which is a paralytic shellfish poisoning toxin as well as okadaic acid and domoic acid (Table 2). A rapid sample preparation procedure was applied to analyze seawater samples from different sampling sites across Europe, and limits of detection of 0.82 ng mL
1, 0.36 ng mL
1, and 166 ng mL
1 were obtained for saxitoxin, okadaic acid, and domoic acid, respectively. McNamee et al. [45] referred that the developed multiplex immunological methods could be used as early warning monitoring tools for a variety of marine biotoxins in seawater samples. 4.2.5. Nutrients It is known that higher the concentrations of nutrients such as nitrite, nitrate, ammonium, phosphate, and silicate in marine waters, higher will be the algae growth and consequently the

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disturbance of water quality [14]. Thus, the monitoring of such nutrients of the marine waters is also of environmental interest. Aravamudhan and Bhansali [49] have developed electrochemical sensors based on doped-polypyrrole nanowires for nitrate detection (in ppm range), which is used as fertilizer in agriculture having negative impacts in marine ecosystems due to the occurrence of eutrophication-algae blooms (Table 2). Aravamudhan and Bhansali [49] have fabricated the electrochemical sensor through electropolymerization of polypyrrole nanowire electrodes, as shown in Fig. 2, obtaining a linear response over the range from 10 mM to 1 mM and a limit of detection of 4.5 mM (Table 2). Lacombe et al. [47] and Aguilar et al. [48] both present electrochemical sensors based on voltammetry for the detection of silicate, and limits of detection lower than 1 mM were obtained (Table 2). 4.2.6. Pharmaceuticals Concerning pharmaceuticals, Ou et al. [50] have developed a biosensor based on SPR to the detection of estradiol in seawater in real time without the need for labeling, where a limit of detection of 0.17 ng mL
1 was obtained. Arvand et al. [51] developed voltammetric sensors based on glassy carbon electrodes modified with carbon nanotubes for the detection of a non-steroidal antiinflammatory drug (diclofenac) in various samples such as seawater. Arvand et al. [51] have obtained good sensitivity in the range of 0.18–119 mM with a limit of detection of 0.04 mM.

4.2.7. Other contaminants Phenols are organic compounds mainly produced in industries, entering in aquatic environments from run-off by industrial and agricultural processing. The in situ monitoring of phenolic compounds in marine waters has been considered as an urgent need due to the inherent toxicity [40]. Malzahn et al. [40] developed practical and in situ sensors based on electrochemical screen-printed electrodes which are integrated in underwater garments for the micromolar detection of phenols (catechol, phenol, and 4-chlorophenol) (Table 2). According to Malzahn et al. [40], the wearable sensors provide a visual indication and alert when the level of contaminants exceeds a pre-defined threshold. Thiocyanate is also used in electroplating industry having hazardous effects in environment. Silva et al. [53] have proposed an optical fiber based methodology for assessment of thiocyanate in seawater (Fig. 2) from 4 to 400 mg L
1, obtaining high performance when compared with a reference methodology (HPLC-UV) with limits of detection of 3 mg L
1 and 4 mg L
1, respectively, and also having a compact design and easy operation (Table 2). Hildebrandt et al. [52] have tested the performance of a portable biosensor for the analysis of chlorpyrifos in water samples such as seawater, which was based on screen-printed electrodes. The biosensor was able to detect pesticide concentrations in the order of the tenth of mg L
1, being comparable to those obtained

Fig. 2. Examples of sensors and biosensors for the monitoring of contaminants in marine waters, with emphasis in their principles of detection. (1) Electrochemical sensor chip (A), actual picture of the electrochemical cell (B), flow-through electrochemical test cell (C), picture of through-flow cell shown with inlet/outlet and PogoTM pin connectors (D) (reprinted from Aravamudhan and Bhansali [49] with permission from Elsevier); (2) (a) schematic representation of the experimental apparatus used for OF based methodology (MP – mobile phase flask; P – pump; I – injector; C – column; AT – analytical tube; OF – optical fiber; W – waste; OC – optical coupler; L – laser diode optical source; PD – photodiode detector; PC – laptop with homemade software); (b) analytical signal obtained by OF based methodology for a standard of thiocyanate (reproduced from Silva et al. [53] with permission from The Royal Society of Chemistry).

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using commercial potentiostats [52]. However, the authors suggested that more studies about the response of the biosensor are needed to determine how it is affected by the composition of the matrix.

[2] [3]

5. Conclusions As mentioned in the Commission Decision on GES criteria, the development of an improved scientific knowledge is of paramount importance, in particular through the EU Marine and Maritime Research Strategy in the framework of the Europe 2020 strategy. Effectively, the European Commission’s Seventh Framework Programme (FP7) and the upcoming Horizon 2020 provide opportunities for initiating relevant marine research in line with the considerations above mentioned. Several European projects are already under development as a support for the EU legislations and guidelines such as MSFD. For example, those included in the FP7 proposed the development of biosensors for real time monitoring of biohazard and man-made chemical contaminants in the marine environment as well as innovative multifunctional sensors for in situ monitoring of marine environment and related maritime activities [10]. Thus, there are already few sensors and biosensors for the continuous monitoring of marine contaminants essentially due to the exigent inter-cooperation of multidisciplinary areas, and results about their application in marine waters are expecting in future publications. The detection of contaminants in the marine environment has already various challenges to be overcome. The sensors and biosensors should be developed to provide continuous monitoring of contaminants rather than detect such substances at a particular sampling site and time. Thus, the problematic of the spatial– temporal variation in marine waters should be overcome though the development of sensing platforms, as an array of sensors and biosensors, for continuous control of physical and chemical characteristics of marine waters. Another challenge is overcoming the difficulty to obtain reproducible results due to the presence of waves, vibrations, and shocks of sensing platforms in real time. Thus, the future perspectives for the development and use of sensors and biosensors for monitoring of marine contaminants are: (a) improvement of the remote control of sensing platforms to the rapid communications of analytical data; (b) development of rapid warming systems in the case of quick contamination; (c) testing the sensors in real seawater with temperature fluctuations and other physical and chemical characteristics found in the real open sea; and (d) development of small, portable, environmentally compatible, robust, inexpensive sensing platforms to monitoring marine contaminants in situ and in real-time. The success of such features could lead to the commercialization of sensing systems, which is the optimal end of the entire process of the fabrication and development of a sensor or a biosensor. Acknowledgments This work was funded by Portuguese Foundation of Science and Technology (FCT) through scholarships (ref. SFRH/BPD/73781/2010 and SFRH/BPD/95961/2013) under QREN-POPH funds, co-financed by the European Social Fund and Portuguese National Funds from MEC. This work was also funded by FEDER under the “Programa de Cooperação Territorial Europeia INTERREG IV B SUDOE” within the framework of the research project ORQUE SUDOE, SOE3/P2/F591. References

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