An Innovative and High-Speed Technology for Seawater Monitoring of Asinara Gulf (Sardinia-Italy)
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Open Journal of Marine Science, 2014, 4, 31-41 Published Online January 2014 (http://www.scirp.org/journal/ojms) http://dx.doi.org/10.4236/ojms.2014.41005 An Innovative and High-Speed Technology for Seawater Monitoring of Asinara Gulf (Sardinia-Italy) Maria Sighicelli1*, Ileana Iocola2, Daniele Pittalis2,3, Antonella Luglié4, Bachisio Mario Padedda4, Silvia Pulina4, Massimo Iannetta1, Ivano Menicucci5, Luca Fiorani5, Antonio Palucci5 1UTAGRI-ECO, ENEA, Roma, Italy 2InTReGA, Spin-Off ENEA, Sassari, Italy 3Department of Territorial Engineering, Geopedology and Applied Geology Section, University of Sassari, Sassari, Italy 4Department of Sciences for Nature and Environmental Resources, University of Sassari, Sassari, Italy 5UTAPRAD-DIM, ENEA, Frascati, Italy Email: *[email protected], [email protected], [email protected], [email protected], [email protected], [email protected], [email protected], [email protected], [email protected], [email protected] Received November 10, 2013; revised December 18, 2013; accepted December 30, 2013 Copyright © 2014 Maria Sighicelli et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. In accor- dance of the Creative Commons Attribution License all Copyrights © 2014 are reserved for SCIRP and the owner of the intellectual property Maria Sighicelli et al. All Copyright © 2014 are guarded by law and by SCIRP as a guardian. ABSTRACT Laser induced fluorescence technique for sea water monitoring allows no-time consuming, non-invasive and non-destructive controls. In this study, the performance of the new shipboard laser spectrofluorometric CAS- PER (Compact and Advanced Laser Spectrometer—ENEA Patent) for monitoring phytoplankton community composition was examined. The prototype CASPER is based on double laser excitation of water samples in the UV (266 nm) and visible (405 nm) spectral region and a double water filtration in order to detect both quantita- tive data, such as chromophoric dissolved organic matter (CDOM), proteins-like components (tyrosine, trypto- phan), algal pigments (chlorophylls a and b, phycoerythrin, phycocyanin, different pigments of the carotenoid groups) and qualitative data on the presence of hydrocarbons and oil pollutants. Sea water samples from differ- ent depths have been collected and analyzed from August 2010 through November 2011 in the Gulf of Asinara (N-W Sardinia). Several sampling stations were selected as sites with different degree of pollution. The accuracy and the reliability of data obtained by CASPER have been evaluated comparing the results with other standard measurements such as: Chlorophyll a (Chl a) data obtained by spectrophotometric method and total phyto- plankton abundance in terms of density and class composition. Spectral deconvolution technique was developed and integrated with CASPER system to assess and characterize a marker pigments and organic compounds in situ and in vivo. Field studies confirmed CASPER system capability to effectively discriminate characteristic spectra of fluorescent water constituents, contributing to decrease the time-consuming manual analysis of the water samples in the laboratory. KEYWORDS Laser Excitation; Deconvolution; Chlorophyll-a; Algal Pigments; Environmental Monitoring 1. Introduction methods of water sampling and laboratory analysis and then additional information is necessary to detect and The oceans and coastal water quality assessment systems identify sources of water contamination, a critical water need to cover large areas with adequate spatial and tem- quality component. poral resolution. Furthermore, the operations must be Several critical components still remain missing or not cost-efficient and involve high-speed data processing. adequately sampled to characterize the marine ecosystem Such requirements are not easily met with traditional biodiversity and habitat change [1]. *Corresponding author. Phytoplankton is an important biotic component and OPEN ACCESS OJMS 32 M. SIGHICELLI ET AL. key biological quality element of the ecological status of liable estimate of the fluorescent constituents in spec- water bodies, according to the Water Framework Direc- trally complex natural waters. This spectral complexity tive (WFD) and the Marine Strategy [2]. It is a sensitive leads to many interpretation problems of the fluorescence bio-indicator of ecosystem general health, its nutrient measurements and compromises the fluorescence as- status, eutrophication, pollutants, and other anthropo- sessments accuracy. To address this issue, recent studies genic impacts in aquatic environments [3]. As primary revealed that it is essential to develop spectral deconvo- producer, it is capable of responding to changes in nutri- lution analysis of the LIF signatures to retrieve informa- ent and toxin input, hydrology, sedimentation, irradiance tion from overlapped spectral patterns of aquatic fluo- and temperature regimes over a wide range of time scales. rescent constituents [9]. Phytoplankton can be subdivided into taxonomic groups The aim of the present work was to investigate the (Chlorophytes, Cryptophytes, Cyanobacteria, Diatoms, performance of the new portable laser apparatus CAS- and Dinoflagellates) that play important roles in coastal PER (Compact and Advanced laser SPE ctrofotometeR primary production, nutrient cycling, and food web dy- —ENEA Patent) for phytoplankton pigments composi- namics. Numerous studies have shown that organic pol- tion analysis, oil derivates detection and seawater quality lution or enhanced nutrient may cause changes on phyto- monitoring in the Gulf of Asinara (N-W Sardinia). plankton taxonomic composition and biomass [4,5]. In The northern coast of Sardinia is one of the most dy- particular, it has been demonstrated that blooms of par- namic and vulnerable environments in the Western Me- ticular species or groups (for example Cyanophyceae, diterranean. It includes the Asinara Island National Park, Dinophyceae) can indicate the occurrence of worse qual- a part of the “Sanctuary of the Cetaceans” of the Medi- ity water [6,7]. terranean Sea and well known beautiful tourist place. The only reliable technique for identifying and enu- Important civil and industrial activities (harbours, power merating phytoplankton species or groups is microscopy and chemical plants) coexist with these high naturalistic [8], a time-consuming and costly procedure that requires quality aspects. a high expertise level. Alternatively, phytoplankton bio- CASPER attempts to improve measurements of chlo- mass may be estimated from photopigment content. rophylls and accessory pigments and organic compounds Chlorophyll a measurements have been used for this contributing to assess phytoplankton physiological/nu- purpose for many years, being considered as a first-level trient status, and to provide basic structural characteriza- indirect indicator of ecosystem eutrophication. tion of phytoplankton community, assessment of CDOM Then, an extended set of phytoplankton characteristics, and water turbidity. These variables offer valuable, cur- including their productivity, photosynthetic capacity, rently missing information for improved bio-environ- physiological status and taxonomic composition, needs to mental characterization of coastal aquatic ecosystems. be monitored for improved ecosystem characterization. In this work, we describe a fluorescence spectral sys- In recent years, the laser induced fluorescence (LIF) tem to detect and assess water fluorescence compounds technique has been widely applied for water quality as- by means of a spectral deconvolution technique, based on sessment in marine and freshwater environment. LIF laboratory and field measurements and implemented in technique allows no-time consuming, non-invasive and open source R software environment non-destructive sampling, without sample pre-treatment. (http://www.rproject.org/), in order to contribute to iden- It is based on the measurements of the laser-induced wa- tify marker pigments and phytoplankton groups using the ter emission to retrieve qualitative and quantitative in- discriminatory capability of characteristic spectra re- formation about the in situ fluorescent constituents [9]. In corded by CASPER. vivo fluorescence of Chlorophyll a and accessory pig- ments (chlorophylls b/c, phycobiliproteins and carote- 2. Material and Methods noids) is generally used as an index of Chlorophyll a 2.1. Study Site and Field Sampling concentration and phytoplankton biomass [10,11] and offers useful information for structural and phytophysi- Field studies for water quality assessment of Gulf of As- ological characterization of the mixed algal populations inara were conducted from August 2010 to November [9,12-14]. 2011. Sea water samples from 0 to 10 m depth were col- Besides the broadband chromophoric dissolved or- lected and analysed by CASPER. ganic matter (CDOM), fluorescence emission can be The stations were situated along six transects perpen- used for assessment of CDOM abundance and its qualita- dicular to the coastline, respectively from more impacted tive characterization [9,15]. areas to less ones, from the town of Porto Torres in the However, many commercially field fluorometers em- central part of the gulf to Cala Reale in the Asinara Is- ploy spectrally broad fluorescence but do not yield an land (Figure 1(a), red points). adequate excitation