Automated preconcentration of Fe, Zn, Cu, Ni, Cd, Pb, Co, and Mn in seawater with analysis using high-resolution sector field inductively-coupled plasma mass spectrometry

Highlights • A rapid automated analytical method for simultaneous analysis of multiple trace metals in small volumes of seawater. • Isotope dilution is utilized for concentration quantification, eliminating sensitivity to variation in recovery. • Minimal variability in automated sample loading and elution volumes allows precise quantification via standard addition for monoisotopic elements. • High accuracy was confirmed by analysis of reference seawaters SAFe S, D1 and D2. • The utilized resin (WAKO) demonstrated improved recoveries for most tested trace metals in comparison to a NOBIAS Chelate-PA1 resin. A rapid, automated, high-throughput analytical method capable of simultaneous analysis of multiple elements at trace and ultratrace levels is required to investigate the biogeochemical cycle of trace metals in the ocean. Here we present an analytical approach which uses a commercially available automated preconcentration device (SeaFAST) with accurate volume loading and in-line pH buffering of the sample prior to loading onto a chelating resin (WAKO) and subsequent simultaneous analysis of iron (Fe), zinc (Zn), copper (Cu), nickel (Ni), cadmium (Cd), lead (Pb), cobalt (Co) and manganese (Mn) by high-resolution inductively-coupled plasma mass spectrometry (HR-ICP-MS). Quantification of sample concentration was undertaken using isotope dilution for Fe, Zn, Cu, Ni, Cd and Pb, and standard addition for Co and Mn. The chelating resin is shown to have a high affinity for all analyzed elements, with recoveries between 83 and 100% for all elements, except Mn (60%) and Ni (48%), and showed higher recoveries for Ni, Cd, Pb, Co and Mn in direct comparison to an alternative resin (NOBIAS Chelate-PA1). The reduced recoveries for Ni and Mn using the WAKO resin did not affect the quantification accuracy. A relatively constant retention efficiency on the resin over a broad pH range (pH 5–8) was observed for the trace metals, except for Mn. Mn quantification using standard addition required accurate sample pH adjustment with optimal recoveries at pH 7.5 ± 0.3. UV digestion was necessary to increase recovery of Co and Cu in seawater by 15.6% and 11.4%, respectively, and achieved full break-down of spiked Co-containing vitamin B12 complexes. Low blank levels and detection limits could be achieved (e.g., 0.029 nmol L⁻¹ for Fe and 0.028 nmol L⁻¹ for Zn) with the use of high purity reagents. Precision and accuracy were assessed using SAFe S, D1, and D2 reference seawaters, and results were in good agreement with available consensus values. The presented method is ideal for high throughput simultaneous analysis of trace elements in coastal and oceanic seawaters. We present a successful application of the analytical method to samples collected in June 2014 in the Northeast Atlantic Ocean

Biogeochemistry of trace metals in European shelf seas

Shelf seas are considered an important source of trace metals (TMs) to the open ocean. However, the processes controlling distributions of dissolved TMs (DTMs) in shelf seas, their seasonal variability and the mechanisms facilitating off-­‐shelf transport to the open ocean are not well constrained. Reported here is the first seasonal study of the DTMs, cadmium (DCd), zinc (DZn), nickel (DNi) copper (DCu) manganese (DMn), cobalt (DCo), aluminium (DAl) and lead (DPb) and their contrasting biogeochemical behaviours in the Celtic Sea continental system. Strong correlations (r2 = 0.91 – 0.97, n = 454) between nutrient-­‐like metals (DCd, DZn, DCu, DNi, DCo (surface waters only)) and macronutrients (phosphate (PO43-­‐) and silicic acid (SiO44-­‐) were observed over all seasons (autumn, spring and summer) indicating that biological uptake in the euphotic zone and remineralization of sinking phytoplankton debris in deeper waters form key controls on their distributions. The correlation between DAl and PO43-­‐ (r2 = 0.80) and SiO44-­‐ (r2 = 0.85) in the upper waters (< 1500 m depth) mimicked the DZn distributions, which was a surprising observation and requires further investigation. Variable DTM ratios relative to PO43-­‐ were observed across different seasons in off-­‐shelf surface waters and for DCd and DZn (full depth profiles) across the continental shelf. Observations from the Celtic Sea region suggest the influence of distinct water masses, phytoplankton community structure and potentially metal specific biogeochemical processes, on DTMs distributions on a seasonal time-­‐scale. Dissolved Co and Mn were more strongly influenced by scavenging and sedimentary inputs. Vertical distributions of DMn showed a typical scavenged type behaviour with enhanced surface waters concentrations from atmospheric inputs combined with photochemical stabilisation. Enhanced DMn and DCo concentrations were observed close to slope sediments and extended away from the shelf at intermediate depths. These observations were related to suspended sediments as indicated by increased signals in turbidity and short-­‐lived 223Ra and 224Ra isotopes (tracers of sediment inputs). This implies that resuspended shelf or slope sediments can act as a source of DMn and DCo that can be transported to the adjacent open ocean. The full depth relationship of DCo with PO43-­‐ revealed a shift in dominant biogeochemical processes controlling DCo vertical distributions in the study region. While biological uptake and remineralization were dominant processes in surface waters, as indicated by a strong correlation with PO43-­‐ (r = 0.89), a gradual decoupling of DCo from PO43-­‐ at intermediate depths was suggestive of progressive scavenging and less pronounced remineralization and a significant negative correlation (r = -­‐0.72) in deeper waters (> 1500 m depth) was suggestive of scavenging as the dominant process at these depths. Beside the natural sources of DTMs, anthropogenic activities have resulted in enhanced DTMs emissions to the environment over the past centuries. Lead has a strong anthropogenic signal as a result of the combustion of leaded fuel and coal. Presented here is the first combined DPb, labile Pb (LpPb) and particulate Pb (PPb) distributions from the Celtic Sea since the phasing out of leaded fuel in Europe. Concentrations of DPb in surface waters have decreased by 4-­‐fold over the last four decades. Nevertheless, a distinct anthropogenic Pb signal was observed from the Mediterranean Sea at intermediate depths, showing that Pb can transported over long distances (>2500 km). Benthic DPb fluxes exceeded the atmospheric Pb fluxes in the region, indicating the importance of sediments as a contemporary Pb source. A strong positive correlation between DPb, PPb and LpPb indicates a dynamic equilibrium between the phases and the potential for particles to ‘buffer’ the DPb pool. This study highlights the requirements of continuing efforts in regulating Pb emissions but also of detailed seasonal TMs studies in coastal systems in future. Results reported here provide insights into distinct biogeochemical processes in oceanographically dynamic shelf seas and demonstrates the potential of Pb in constraining ocean circulation patterns

Biogeochemistry of trace metals in European shelf seas

Shelf seas are considered an important source of trace metals (TMs) to the open ocean. However, the processes controlling distributions of dissolved TMs (DTMs) in shelf seas, their seasonal variability and the mechanisms facilitating off-­‐shelf transport to the open ocean are not well constrained. Reported here is the first seasonal study of the DTMs, cadmium (DCd), zinc (DZn), nickel (DNi) copper (DCu) manganese (DMn), cobalt (DCo), aluminium (DAl) and lead (DPb) and their contrasting biogeochemical behaviours in the Celtic Sea continental system. Strong correlations (r2 = 0.91 – 0.97, n = 454) between nutrient-­‐like metals (DCd, DZn, DCu, DNi, DCo (surface waters only)) and macronutrients (phosphate (PO43-­‐) and silicic acid (SiO44-­‐) were observed over all seasons (autumn, spring and summer) indicating that biological uptake in the euphotic zone and remineralization of sinking phytoplankton debris in deeper waters form key controls on their distributions. The correlation between DAl and PO43-­‐ (r2 = 0.80) and SiO44-­‐ (r2 = 0.85) in the upper waters (< 1500 m depth) mimicked the DZn distributions, which was a surprising observation and requires further investigation. Variable DTM ratios relative to PO43-­‐ were observed across different seasons in off-­‐shelf surface waters and for DCd and DZn (full depth profiles) across the continental shelf. Observations from the Celtic Sea region suggest the influence of distinct water masses, phytoplankton community structure and potentially metal specific biogeochemical processes, on DTMs distributions on a seasonal time-­‐scale. Dissolved Co and Mn were more strongly influenced by scavenging and sedimentary inputs. Vertical distributions of DMn showed a typical scavenged type behaviour with enhanced surface waters concentrations from atmospheric inputs combined with photochemical stabilisation. Enhanced DMn and DCo concentrations were observed close to slope sediments and extended away from the shelf at intermediate depths. These observations were related to suspended sediments as indicated by increased signals in turbidity and short-­‐lived 223Ra and 224Ra isotopes (tracers of sediment inputs). This implies that resuspended shelf or slope sediments can act as a source of DMn and DCo that can be transported to the adjacent open ocean. The full depth relationship of DCo with PO43-­‐ revealed a shift in dominant biogeochemical processes controlling DCo vertical distributions in the study region. While biological uptake and remineralization were dominant processes in surface waters, as indicated by a strong correlation with PO43-­‐ (r = 0.89), a gradual decoupling of DCo from PO43-­‐ at intermediate depths was suggestive of progressive scavenging and less pronounced remineralization and a significant negative correlation (r = -­‐0.72) in deeper waters (> 1500 m depth) was suggestive of scavenging as the dominant process at these depths. Beside the natural sources of DTMs, anthropogenic activities have resulted in enhanced DTMs emissions to the environment over the past centuries. Lead has a strong anthropogenic signal as a result of the combustion of leaded fuel and coal. Presented here is the first combined DPb, labile Pb (LpPb) and particulate Pb (PPb) distributions from the Celtic Sea since the phasing out of leaded fuel in Europe. Concentrations of DPb in surface waters have decreased by 4-­‐fold over the last four decades. Nevertheless, a distinct anthropogenic Pb signal was observed from the Mediterranean Sea at intermediate depths, showing that Pb can transported over long distances (>2500 km). Benthic DPb fluxes exceeded the atmospheric Pb fluxes in the region, indicating the importance of sediments as a contemporary Pb source. A strong positive correlation between DPb, PPb and LpPb indicates a dynamic equilibrium between the phases and the potential for particles to ‘buffer’ the DPb pool. This study highlights the requirements of continuing efforts in regulating Pb emissions but also of detailed seasonal TMs studies in coastal systems in future. Results reported here provide insights into distinct biogeochemical processes in oceanographically dynamic shelf seas and demonstrates the potential of Pb in constraining ocean circulation patterns

Competitive Interactions Between Microbial Siderophores and Humic-Like Binding Sites in European Shelf Sea Waters

Siderophores are low molecular weight high affinity iron chelates found at low concentrations in seawater. In this study we determined the total concentrations and identities of siderophores in extracts isolated from a shelf sea environment on the Northwest European shelf by high performance liquid chromatography coupled to high resolution inductively coupled plasma mass spectrometry (ICP-MS) in parallel to high resolution electrospray ionisation mass spectrometry (ESI-MS). We identified a total of 24 different siderophores in our samples via metal isotope profiling of masses detected by ESI-MS. Twenty three of the identified siderophores could be assigned to three siderophore families – ferrioxamines, amphibactins and marinobactins. In contrast, only 12 peaks could be resolved in iron chromatograms obtained via ICP-MS analysis. Comparison of results obtained by the two mass spectrometry detectors showed that neither method was able to detect and identify all siderophores present in the samples on its own. We assessed the impact of our observed total siderophore concentrations on iron speciation by calculating the distribution of iron species as a function of total siderophore concentrations at different iron concentrations representative of our study area. We considered competition for iron between siderophores, a humic like dissolved organic matter (DOM) fraction and hydroxide ions by combining an ion-pair model with a non-ideal competitive interaction (NICA)-Donnan model. We found that the overall impact of siderophores on iron biogeochemistry is low at concentrations of siderophore <100 pmol L-1, and that the dominant iron species present at siderophore concentrations of the order of a few tens of pmol L-1 will be iron bound to the humic like DOM fraction. Furthermore the heterogeneity of binding sites in the humic like DOM fraction means that other binding sites present in organic matter could be effective competitors for siderophores, especially at low iron concentrations. Our findings highlight the importance of binding site heterogeneity when considering the influence of different iron binding groups on iron speciation in the marine environment

Physical and biogeochemical controls on seasonal iron, manganese, and cobalt distributions in Northeast Atlantic shelf seas

Dissolved (<0.2 μm) trace metals (dTMs) including iron (Fe), manganese (Mn), and cobalt (Co) are micronutrients that (co-) limit phytoplankton growth in many ocean regions. Here, we present the spatial and seasonal distributions of dFe, dMn, and dCo on the Northeast Atlantic continental margin (Celtic Sea), along a transect across the shelf and two off-shelf transects along a canyon and a spur. Waters on the continental shelf showed much higher dTM concentrations (dFe 0.07–6.50 nmol L−1, average 1.41 ± 0.96 nmol L−1, n = 138; dMn 0.868–14.8 nmol L−1, 2.75 ± 2.37 nmol L−1, n = 148; dCo 54.8–217 pmol L−1, 109 ± 32 pmol L−1, n = 144) than on the slope (dFe 0.03–1.90 nmol L−1, 0.65 ± 0.43 nmol L−1, n = 454; dMn 0.223–1.14 nmol L−1, 0.58 ± 0.20 nmol L−1, n = 458; dCo 27.3–122 pmol L−1, 71.7 ± 11.7 pmol L−1, n = 441), attributed to strong dTM contributions from a low-salinity endmember, i.e., riverine discharge. Benthic sedimentary input via reductive dissolution (especially for dFe and dMn), delineated by short-lived radium (Ra) isotopic activities (223Raxs and 224Raxs), was only prominent at a station (Site A) characterized by fine sediments. On the continental slope, dMn levels at depth were mainly determined by the formation of insoluble Mn oxides and the intrusion of Mediterranean Outflow Waters. In contrast, dFe and dCo concentrations at depth were balanced by the regeneration from remineralization of sinking organic particles and scavenging removal. In addition, bottom and intermediate nepheloid layers along the slope illustrated both elevated dTM concentrations and Ra isotopic activities. The presence of nepheloid layers is especially significant along the canyon transect relative to the spur transect, demonstrating the importance of slope topography on the off-shelf transport of dTMs into the Northeast Atlantic Ocean. As a seasonal stratified shelf sea, dTMs and nutrients showed synchronized seasonal variations on the shelf, indicating the influence of biological processes in addition to source effects. Surface dFe and dCo were depleted in summer due to enhanced biological uptake, while sub-surface dFe and dCo were elevated in summer and autumn ascribed to the remineralization of sinking organic particles. In contrast, surface dMn levels were predominantly controlled by the seasonal variations in photoreduction, while sub-surface dMn concentrations were relatively constant throughout the year. The combined effects of fluvial and benthic sources, topographical controls, and biological processes shape the seasonal variations of dTM distributions. Such seasonal variations in dTMs and biological activities can affect the biological carbon pump on the Northeast Atlantic continental margin, and may further influence the carbon cycle in the Atlantic Ocean via the dynamic dTM exchange between continental margins and the open ocean

Ocean circulation and biological processes drive seasonal variations of dissolved Al, Cd, Ni, Cu, and Zn on the Northeast Atlantic continental margin

Nutrients and nutrient-like dissolved trace metals (dTMs) are essential for the functioning of marine organisms and therefore form an important part of ocean biogeochemical cycles. Here, we report on the seasonal distributions of dissolved zinc (dZn), nickel (dNi), copper (dCu), cadmium (dCd), aluminum (dAl), and nutrients on the Northeast Atlantic continental margin (Celtic Sea), which is representative for temperate shelf seas globally. Variations in surface water dTM and nutrient concentrations were mainly regulated by seasonal changes in biological processes. The stoichiometry of dTMs (especially for dCu and dZn) and nutrients on the continental shelf was additionally affected by fluvial inputs. Nutrients and dTMs at depth on the continental slope were determined by water mass mixing driven by ocean circulation, without an important role for local remineralization processes. The Mediterranean Outflow Waters are especially important for delivering Mediterranean-sourced dTMs to the Northeast Atlantic Ocean and drive dTM:nutrient kinks at a depth of ~1000 m. These results highlight the importance of riverine inputs, seasonality of primary production and ocean circulation on the distributions of nutrients and nutrient-like dTMs in temperate continental margin seas. Future climate related changes in the forcing factors may impact the availability of nutrients and dTMs to marine organisms in highly productive continental shelf regions and consequently the regional carbon cycle

Laatujohtaminen valmistavassa teollisuudessa : Toimintajärjestelmän uudistaminen

Opinnäytetyön toimeksiantajana oli Savonlinnassa toimiva lujitemuovituotteisiin erikoistunut valmistusyritys Oy Esmarin Composites Ltd. Yrityksellä on ollut SFS-EN ISO 9001:2008 -mukainen sertifiointi vuodesta 2012. Yrityksen laatujärjestelmä kattaa kaikki yrityksen toiminnot, ja ne on dokumentoitu toimintakäsikirjaan. Opinnäytetyön tavoitteena oli perehtyä laatujohtamiseen valmistavassa teollisuudessa ja uudistaa yrityksen toimintajärjestelmää. Yrityksen selainpohjaisella alustalla oleva toimintakäsikirja liitteineen siirrettiin uudelle alustalle. Toimenpiteen tavoitteena oli toimintakäsikirjan käytön selkeyttäminen ja maksullisesta selainpohjaisesta dokumentoinnista eroon pääseminen. Toimintakäsikirjan ja sen liitteiden uusiksi alustoiksi valikoituivat Microsoft Office –ohjelmistot yleisyytensä vuoksi. Toimintakäsikirjan tekstidokumentaatioiden ulkoasu päivitettiin ja tarvittavia tiedonkeruulomakkeita tehtiin Microsoft Wordin ja Excelin avulla; muun muassa poikkeamista johtuvien kustannusten seurantaan asiakaskohtaisesti tehtiin Excelillä toimiva tiedonkeruumenetelmä. Opinnäytetyön teon aloitusajankohdan vuoksi opinnäytetyössä ei ole vielä otettu huomioon SFS-EN ISO 9001:2015:n päivityksiä. Yrityksen on nyt kuitenkin selkeämmän dokumentaation avulla helpompi päivittää johtamisjärjestelmäänsä uusien vaatimuksien mukaiseksi.This thesis was commissioned by Oy Esmarin Composites Ltd. The company specializes in the manufacture of reinforced plastic products and the company has had ISO 9001:2008 standardization since 2012. The company’s quality management system covers all the company’s operations and they are documented in the operations manual. Aim of this thesis was familiarize to quality management in the manufacturing industry and transfer the company’s web-based platform operating manual with attachments to a new platform. The purpose was to clarify the use of the operations manual and replace the browser-based documentation. Microsoft Office software was selected to new platform for the operations manual and its attachments, because they are public software. The layout of the operations manual was updated and the necessary data collection forms were made in Microsoft Word and Excel, for example a separate Excel program was made to calculate the cost of deviations. Because this thesis was started in the beginning of the year 2015 update from ISO 9001:2008 standard to ISO 9001:2015 has not yet been taken into consideration. The company’s operations manual is now clearer and easy to use so updating the management system according to the requirements is easier