WIXLIB

(2016)The studied sediments were mostly sandy silts with TOC,TN, TS and TIC contents that are characteristic of the studyarea. Two facies could be defined in core SS10T01: theupper one (0-13.5 cm) which comprised dark-coloredsediments with higher TOC and TS contents than the lowerone (13.5-27 cm), with light-colored sediments and higherTIC contents. A similar facies distribution was observed incore SS10T03 (two facies: 0-16.5 cm, and below), but withan additional coarse-sand layer near its bottom (Fig. 1).Sediments are oxic until 2.5 cm, and then, suboxic. No Pbwas detected in pore waters ( 0.200 µg L-1), where sulfatecontent decreased with depth and sulfide content were lowor non-detectable. Lead total concentration was extremelyhigh, being higher in the upper facies ( 4.9%, coincidentwith higher TOC contents) than in the lower facies ( 2.1%)of core SS10T01 (Fig. 1). Pb profiles obtained with theItrax and conventional techniques (ICP-OES and XRF)were very similar, with the advantage of the former in lesstime consumption and sample pretreatment. Similar highPb levels were observed for core SS10T03. The highresolution Itrax data shown a high Pb variability in bothcores (57,950 22,320 peak area in SS10T01 and56,500 21,200 p.a. in SS10T03) and also a markedsubsurficial maxima (Fig. 1). This maxima is coincidentwith relatively high Ag, As, Cu and Zn contents. This isprobably due to the use of Zn oxide in the ceramic, As inits glaze, and Ag-thread in the decoration of some pieces.a)0.400.80206Pb (%)AGS (mm)0.001.200.0 2.0 4.0 6.0 8.0 ecovPbICP20ACKNOWLEDGEMENTS1.0 1.5 2.0 2.5 3.0 3.5b)0.00040000 80000 120000TOC (%)Pb (p.a.)AGS (mm)Pb (p.a.)0.400.80glazing10gypsumDepth (cm)01.200Pbxs (Bq kg-1)21040000 80000 pth (cm)that of total Pb (Fig. 1). Then, high quantities of Pb areadsorbed onto sedimentary particles, forming insolublesalts and organic complexes, which are environmentallyavailable. Profiles of Pb stable ratios for the bioavailableand recoverable fractions and the total Pb content weresimilar, with a marked minimum at 11 cm (Fig. 1). Theseratios were very similar to the characteristic ratios ofgypsum from the ceramic factory [3]. The anthropogenicPb represents 99.8-99.9% of total Pb, the main input beingthe ceramic industry, with a small contribution from petrolcombustion ( 4%).Radionuclide profiles showed a clear grain-size influence,with a marked increase toward the bottom core (Fig. 1)probably due to higher contents of organic matter and finegrained sediments. Due to this the 137Cs specific activityprofile was normalized by the Fe content. Three relativemaximum were detected (Fig. 1). The first two wereconsidered time-markers (1987 and 1963), the lastdiscarded due to the described matrix-effect. The agemodel was established by applying the CRS-MV model tothe in excess 210Pb specific activity profile [2] andsedimentation rates of 7.6 mm a-1 were obtained. Whensediment cores from former studies are compared to thestudied cores [2,5] it was detected a relative displacementof some characteristic features in the 137Cs specific activityprofile and in the total Pb content profile that could be usedas time markers, and then, sedimentation rates of the sameorder ( 5-7 mm a-1) are obtained. According to thecorroborated chronology the studied sediments spans thelast 60 years. The Pb total profile show the starting of theceramic industry around 1972, with maximum dischargesaround the beginning of the 1990s, and the persistence ofvery high Pb levels in 2010, in spite of the industry closurein 2001.20This work was supported by the projects 12022PR (XUGA). I. Rodríguez-Germade wasfunded by a FPU scholarship (MECD) and P. ÁlvarezIglesias by the Ángeles Alvariño program (XUGA).REFERENCES304001020304050Water content (%)0.00.40.81.21.6(137Cs / Fe)*103Fig. 1. Depth-wise profiles of: a) average grain size (AGS),TOC, Pb concentration and 206Pb/207Pb in the bioavailable,recoverable and total fractions (by ITRAX and ICP-OES)in core SS10T01; and b) mean grain size, water content,total Pb content (ITRAX), 210Pb in excess and 137Cs Fenormalized specific activities in core SS10T03.Regarding the distribution of these high Pb levels detected,18% was recovered in the bioavailable fraction and 56% inthe recoverable fraction –their respective profiles similar to1 - Prego R., Cobelo-García, A, 2003. Twentieth centuryoverview of heavy metals in the Galician Rias (NW IberianPeninsula). Environ Pollut, 121: 425-452.2 - Álvarez-Iglesias P, Quintana B, Rubio B, Pérez-ArluceaM, 2007. Sedimentation rates and trace metal input historyin intertidal sediments from San Simón Bay (Ría de Vigo,NW Spain) derived from 210Pb and 137Cs chronology. JEnviron Radioact 98: 229-250.3 - Álvarez-Iglesias P, Rubio B, Millos J, 2012. Isotopicidentification of natural vs. anthropogenic lead sources inmarine sediments from the inner Ría de Vigo (NW Spain).Sci Tot Environ 437: 22-35.10

(2016)4 - Catalogue of National Water Research Institute, 2006.Certified Reference Materials & Quality AssuranceServices. Canada Centre for Inland Waters NationalLaboratory for Environmental Testing Burlington, Ontario,Canada, v 5.7.11

(2016)20th century overview of industrial impact through trace elements content insediments from the Ria of Ferrol (NW Iberian Peninsula)M.A. Álvarez-Vázquez1,2, R. Prego1, P. Álvarez-Iglesias3, M.C. Pedrosa-García4, S. Calvo1,E. De Uña-Álvarez2, B. Quintana4, C. Vale5,6, M. Caetano5,61Instituto de Investigaciones Marinas (IIM-CSIC), 36208 Vigo, Spain.Grupo GEAAT, Área de Geografía Física (University of Vigo), 32004 Ourense, Spain.3Grupo GEOMA, Faculty of Marine Sciences (University of Vigo), 36310, Vigo, Spain.4Laboratorio de Radiaciones Ionizantes (LRI), Faculty of Sciences (University of Salamanca), 37008 Salamanca, Spain.5Instituto Português do Mar e da Atmosfera (IPMA), 1449-006 Lisboa, Portugal.6Interdisciplinary Centre for Marine and Environmental Research (CIIMAR/CIMAR), 4050-123 Porto, Portugal.2ABSTRACTThe Ría of Ferrol (Galicia, Spain) has hosted an important shipbuilding activity since the mid-18th century. Therelease of trace elements to the system is closely related to the history and changes in the industrial sector. Tomake an assessment of the changing impact, a short sediment core (50 cm depth) was recovered in the intertidalestuarine area of the Grande-de-Xubia River, the main stream draining into the ria. Layers of 2 cm thickness offine sediments were separated and dried. Contents Al (normalizer element), Cd, Co, Cr, and Cu were determinedin each layer. The core was also dated by 210Pb γ-emission. Preindustrial layers were not achieved so, in order toset a baseline, a comparison was made with data from the nearby Ria of Ares (close to a natural state). By usingthe metal-Al relationships of this second dataset, the enrichment factor (EF), indicative of human pressure, wascalculated for each sample. These elements presented different degrees of enrichment and contamination. Theincreasing order during the 20th century was as follows: negligible contamination for Cr, moderate contaminationfor Co, severe contamination for Cd, and heavy contamination for Cu.INTRODUCTIONSediments, accumulated in estuaries over the time, are arecord of the water quality in the time when materialsprecipitated. These sediments have a natural componentwith origin in the rocks and soils within the river drainagebasin mainly, also by the activity of living organisms.Since the Industrial revolution it is especially important theinput of waste materials from human activities, which have“severely” affected many estuaries [1] being now amongthe most impacted environments in the World [2] of theAnthropocene. Trace elements (TEs) are naturally presentin sediments but, nowadays, their contents were noticeablyaltered by anthropogenic contributions especially in coastalareas where the human activity is intense, so they can beused as tracers of human impact, by themselves and, alsoby their association with other kind of contaminants.The study of TEs in sediment cores, coupled with somegeochronology technique, allows the reconstruction of thehistorical relationship between humans and estuaries, beingcritical to first establish natural background values [3] tomake an assessment of the magnitude and evolution of thehuman impact.This communication presents a quick view of the historicalhuman impact, during the 20th century, in one of the mostindustrialized areas of Galicia (NW Iberian Peninsula),namely the Ria of Ferrol. The shipyard industry, settled inthe shore of this ria in the 18th century, has evolved andreached its peak in the mid-20th century.Fig. 1. Location map. Hydrographic information fromAugas-de-Galicia Co. Basemaps 2014 ESRI.12

(2016)MATERIAL AND METHODSThe sediment core was sampled using a hand-driven GougeAugers Sampler in July 2012 during low tide. Thesampling point was in the estuary of the Grande-de-XubiaRiver (Ria of Ferrol), in an area without apparentbioturbation. Cores were on site divided into 2 cm layers.Muddy samples were oven-dried. After acid digestion, Alwas analysed by Flame Atomic Absorption Spectrometry(Varian SpectrAA 220 FS) in the Marine Biogeochmistrylaboratory, IIM-CSIC (Spain); Cadmium, Co, Cr and Cu byMass Inductively Coupled Plasma (Thermo-Elemental Xseries) in the Environmental Oceanography laboratory,IPMA (Portugal). The cores were also dated by 210Pb γemission in the Ionizing Radiation Laboratory (LRI),University of Salamanca (Spain). All procedures duringsampling, processing and analysis were performed usingtrace metal clean techniques, and analytical results checkedby the use of certificate reference materials.RESULTS AND DISCUSSIONThe TEs contents in the core ranged 0.39-1.26 mgCd·kg-1,9.9-28.0 mgCo·kg-1, 71-127 mgCr·kg-1 and 72-284mgCu·kg-1. The highest extremes of the four elements areover the ranges for unpolluted marine sediments [4] and thebackground for estuaries in the same regional area [5], butthe contents of Co are withing the ranges for Galician soilsover granitic rocks [6] (dominant lithology in the Grandede-Xubia River basin). In consequence, these TEs aresuspicious of being human-enriched but the local lithologymay play a critical role in determining the extent of theanthropogenic influence, a local reference is needed.Since the core did not reach a preindustrial layer, in orderto compare with local background values, data from thenearby Ria of Ares was used for comparison, because thisria drainage area is composed by a similar lithology and thecontents of TEs in the sediments of the Eume River estuary(see Fig. 1) were previously set as close to a natural state(unpublished data). In order to avoid possible differences inparticle size, Al was chosen as normalizer element. Anenrichment factor (EF) was calculated as the quotientbetween the TE-Al relationship (TE content divided by theAl content) in each sample of the core from Ferrol and theaverage TE-Al relationship in the background reference(Ares), according to the following equation:EF ([TE]/[Al])Ferrol/([TE]/[Al])ReferenceThe calculated EFs for each layer of the core, jointly withthe results of the 210Pb dating, which allows building thetimeline, are presented in Fig. 2. To evaluate de degree ofanthropogenic impact a contamination criteria [7] wasused, selected categories in increasing degree ofcontamination are: EF 1 negligible, 1 EF 2 possible,2 EF 3 moderate, 3 EF 6 severe, 6 EF 9 very severeand EF 9 heavy.Fig. 2. Time variation of EFs and contamination criteria.The four elements presented the same pattern ofenrichment’s heights and troughs, being the highestenrichments around the 1950s when the industry blossomswith the implementation of great oil-tankers building. TheEFs also reflects the beginning of modern shipbuilding in1908 and the industry-decay after the 60s, when the sectorfell into crisis. In the 90s the industry was reactivated andEFs rose again. Currently (2012), Cr and Co did notpresent contamination (EFs were 0.9 and 1.1 respectively),contamination due to Cu was moderate (2.8), and Cu (3.4)remains in the range of severe contamination.ACKNOWLEDGEMENTSThis study from the project “Land-sea exchange of tracemetals and its importance for marine phytoplankton in anupwelling coast”, ref. CTM2011-28792-C02, was financedby MINECO CES1 - Meybeck M, Vörösmarty C, 2005. Fluvial filtering ofland-to-ocean fluxes: From natural Holocene variations toAnthropocene. CR Geosci. 337:107-123.2 - Birch GF, Gunns TJ, & Olmos M, 2015. Sedimentbound metals as indicators of anthropogenic change inestuarine environments. Mar. Poll. Bull. 101(1):243-257.3 - Álvarez-Iglesias P, Rubio B, & Pérez-Arlucea M, 2006.Reliability of subtidal sediments as “geochemicalrecorders” of pollution input: San Simón Bay (Ría de Vigo,NW Spain). Estuar. Coas. Shelf. S. 70(3):507-521.4 - Prego R, & Cobelo-Garcıa A, 2003. Twentieth centuryoverview of heavy metals in the Galician Rias (NW IberianPeninsula). Environ. Poll. 121(3):425-452.5 - Carballeira A, Carral E, Puente X, & Villares R, 2000.Regional-scale monitoring of coastal contamination.Nutrients and heavy metals in estuarine sediments andorganisms on the coast of Galicia (northwest Spain). Int. J.Environ. Pollut. 13(1-6):534-572.6 - Macías-Vázquez F, & Calvo de Anta R, 2009. NivelesGenéricos de referencia de metales pesados y otroselementos traza en suelos de Galicia. Xunta de Galicia.7 - Álvarez-Vázquez MA, Bendicho C, & Prego R, 2014.Ultrasonic slurry sampling combined with total reflectionX-ray spectrometry for multi-elemental analysis of coastalsediments in a ria system. Microchem. J. 112:172-180.13

(2016)River-ria fluxes of dissolved trace elements:pristine versus anthropogenic disturbed contributionsMiguel Ángel Álvarez-Vázquez1,2, Ricardo Prego1, Miguel Caetano3, Elena De Uña-Álvarez21Instituto de Investigaciones Marinas (CSIC). 36208 Vigo, Spain.Área de Geografía Física, Grupo GEAAT, Campus de Ourense (UVigo). 32004 Ourense, Spain.3Instituto Português do Mar e da Atmosfera (IPMA). 1449-006 Lisboa, Portugal.2ABSTRACTLittle information is available about how the land-sea contributions of pristine small world-rivers may vary incontaminated conditions. Therefore, a comparison of fluvial discharges of dissolved trace elements wasperformed in the Ria of Cedeira (NW Iberian Peninsula). Along a hydrological year samples were taken in themain streams draining into the ria: the pristine Das-Mestas, the Condomiñas affected by sewage discharges, andthe Forcadas having a reservoir for water supply on its course. Daily flow data were provided by “Augas-deGalicia” and EMAVISA. Concentrations of dissolved trace elements were determined by ICP-MS. Cleantechniques were used. Precision and accuracy was checked by the analysis of CRM. River-ria fluxes werequantified by a ratio estimator method derived from the Beale’s ratio estimator. Obtained results distinguishthree main concentration groups in the three rivers: (a) Al, As, Cr, Fe and Pb presented higher ranges in theCondomiñas and lower in the Forcadas; (b) Cd, Cu and Mn were higher in Condomiñas and Ferreiras,; (c) Coand Ni in Condomiñas were over those in the other two rivers. Mo presented similar ranges but two high outliersin the Condomiñas. Thus, the reservoir influence depicted a river-ria flux decrease while sewage contributionsincreased the river flux of trace elements.INTRODUCTIONThe study of the interactions between land and ocean hasgained interest in recent decades. This growing interestincludes the recommendation of LOICZ program toincorporate the study of river inputs in the assessment ofcoastal dynamics [1]. These authors state that theconstruction of dams, deforestation, rising rates ofurbanization and overexploitation of water resources havecaused a change in river flows and the matter transportedby fluvial water. It is

one (13.5-27 cm), with light-colored sediments and higher TIC contents. A similar facies distribution was observedin core SS10T03 (two facies: 0-16.5 cm, and below), but with an additional coarse-sand layer near its bottom (Fig. 1). Sediments are oxic until 2.5 cm, and then, suboxic. No Pb was detected in pore waters ( 0.200 µg L-1), where sulfate