Dissolved trace elements and nutrients in the North Sea-a current baseline.

Primary production is an important driver of marine carbon storage. Besides the major nutrient elements nitrogen, phosphorus, and silicon, primary production also depends on the availability of nutrient-type metals (e.g., Cu, Fe, Mo) and the absence of toxicologically relevant metals (e.g., Ni, Pb). Especially in coastal oceans, carbon storage and export to the open ocean is highly variable and influenced by anthropogenic eutrophication and pollution. To model future changes in coastal carbon storage processes, a solid baseline of nutrient and metal concentrations is crucial. The North Sea is an important shelf sea, influenced by riverine, atmospheric, Baltic Sea, and North Atlantic inputs. We measured the concentrations of dissolved nutrients (NH4+, NO3-, PO43-, and SiO44-) and 26 metals in 337 water samples from various depths within the entire North Sea and Skagerrak. A principal component analysis enabled us to categorize the analytes into three groups according to their predominant behavior: tracers for seawater (e.g., Mo, U, V), recycling (e.g., NO3-, PO43-, SiO44-), and riverine or anthropogenic input (e.g., Ni, Cu, Gd). The results further indicate an increasing P-limitation and increasing anthropogenic gadolinium input into the German Bight.

Determination of technology-critical elements in seafood reference materials by inductively coupled plasma-tandem mass spectrometry.

The certified reference materials (CRMs) BCR-668 (mussel tissue), NCS ZC73034 (prawn), NIST SRM 1566a (oyster tissue) and NIST SRM 2976 (mussel tissue) were analyzed for their mass fractions of 23 elements using inductively coupled plasma tandem-mass spectrometry (ICP-MS/MS). This study focused on the quantification of selected technology-critical elements (TCEs), specifically rare earth elements (REE) and the less studied TCEs Ga, Ge, Nb, In and Ta. Microwave assisted closed vessel digestion using an acid mixture of HNO3, HCl and H2O2 was applied to varying sample masses and two different microwave systems. Recoveries of 76% (Gd, NCS ZC73034) to 129% (Lu, BCR-668) were obtained for the REE and 83% (Ge, NCS ZC73034) to 127% (Nb, NCS ZC73034) for the less studied TCEs across all analyzed CRMs (compared to certified values) using the best-performing parameters. Mass fractions for all analyzed, non-certified elements are suggested and given with a combined uncertainty U (k = 2), including mass fractions for Ga (11 µg kg-1 ± 9 µg kg-1 to 67 µg kg-1 ± 8 µg kg-1) and In (0.4 µg kg-1 ± 0.3 µg kg-1 to 0.8 µg kg-1 ± 0.7 µg kg-1). This study provides mass fractions of possible new emerging contaminants and addresses the relevant challenges in quantification of less studied TCEs, thus allowing the application of existing CRMs for method validation in studies dealing with the determination of TCEs in seafood or other biota.

Investigation of potential metal emissions from galvanic anodes in offshore wind farms into North Sea sediments.

To evaluate potential metal emissions from offshore wind farms (OWFs), 215 surface sediment samples from different German North Sea OWFs taken between 2016 and 2022 were analyzed for their mass fractions of metals and their isotopic composition of Sr. For the first time, this study provides large-scale elemental data from OWFs of the previously proposed galvanic anode tracers Cd, Pb, Zn, Ga and In. Results show that mass fractions of the legacy pollutants Cd, Pb and Zn were mostly within the known variability of North Sea sediments. At the current stage the analyzed Ga and In mass fractions as well as Ga/In ratios do not point towards an accumulation in sediments caused by galvanic anodes used in OWFs. However, further investigations are advisable to evaluate long-term effects over the expected lifetime of OWFs, especially with regard to the current intensification of offshore wind energy development.

Impact of storage temperature and filtration method on dissolved trace metal concentrations in coastal water samples.

Trace elements play a major role in biogeochemical cycles and oceanographic processes. To determine trace element concentrations, the dissolved and particulate phase are usually separated by filtration. However, the frequently used membrane filtration as well as sample storage can bias the dissolved elemental concentrations by adsorption or desorption/contamination. We present a comparison of two filtration methods for coastal and estuarine water samples (pressure filtration with Nuclepore™ polycarbonate filters, vacuum filtration with DigiFILTER™s) applied to aliquots of a large-volume coastal water sample that were stored at -18°C or 4°C for up to nine weeks. The filtrates were analyzed by seaFAST-ICP-MS for dissolved Cd, Ce, Co, Cu, Dy, Er, Eu, Fe, Ho, La, Mn, Mo, Nd, Pb, Pr, Sm, Tb, U, V, W, Y, and Zn. The filtration blanks of DigiFILTER™s (0.0006 ± 0.0010 ng L-1 for Ho to 110 ± 180 ng L-1 for Zn) were sufficiently low for quantification of all analyzed elements with good repeatability, enabling a fast and reliable filtration of large sample sets of coastal water. However, the findings also highlight the need to measure procedural blanks including the filtration instead of only the instrument blanks to validate results. Measured concentrations of both filtration methods did not differ significantly for Cd, Cu, Mo, U, V, W, Zn but for other investigated elements, the ratio between both methods was up to 1.8 for Ce and 4.1 for Fe. Within nine weeks of storage, the elemental concentrations decreased significantly, resulting in losses of 20% Mn in frozen samples and 63% Pb, 64% Co and 93% Mn in cooled samples. PRACTITIONER POINTS: Two fast and cheap filtration methods for coastal water samples were compared. Dissolved concentrations of 22 elements were measured by seaFAST-ICP-MS. The filtration method is important in addition to filter pore size. Filtration blanks need to be reported to maintain comparability between methods. Cool and frozen storage of water samples biases the dissolved metal concentration.

Quantification and characterization of microplastics in surface water samples from the Northeast Atlantic Ocean using laser direct infrared imaging.

15 filtration samples were collected at eight locations onboard the RV Sonne (cruise SO279 in 2020) from 6 m water depth using a fractionated stainless-steel filtration unit. The size fraction > 300 µm was visually examined and potential microplastic particles were analyzed by ATR-FTIR spectroscopy. The treatment of size class 20 µm < d < 300 µm was based on enzymatic-oxidative microwave-assisted "one-pot" matrix digestion in conjunction with analysis of the microplastics by time-efficient LDIR imaging. Total number concentrations ranged from 47 to 2154 microplastic particles per m3 (average for all stations: 500 ± 700 microplastic particles m-3 (1 SD; n = 8)). In total, 20 polymer types were identified. The most common polymer types were polyethylene terephthalate (20 %) and acrylates/polyurethane/varnish (15 %). 93 % of the detected microplastics were smaller than 100 µm in length. Analysis of sample replicates indicates high spatio-temporal variations in microplastic pollution within the investigated region.

Laser microdissection pressure catapulting (LMPC): a new technique to handle single microplastic particles for number-based validation strategies.

This study examines laser microdissection pressure catapulting (LMPC) as an innovative method for microplastic research. Laser pressure catapulting as part of commercially available LMPC microscopes enables the precise handling of microplastic particles without any mechanical contact. In fact, individual particles with sizes between several micrometers and several hundred micrometers can be transported over centimeter-wide distances into a collection vial. Therefore, the technology enables the exact handling of defined numbers of small microplastics (or even individual ones) with the greatest precision. Herewith, it allows the production of particle number-based spike suspensions for method validation. Proof-of-principle LMPC experiments with polyethylene and polyethylene terephthalate model particles in the size range from 20 to 63 µm and polystyrene microspheres (10 µm diameter) demonstrated precise particle handling without fragmentation. Furthermore, the ablated particles showed no evidence of chemical alteration as seen in the particles' IR spectra acquired via laser direct infrared analysis. We propose LMPC as a promising new tool to produce future microplastic reference materials such as particle-number spiked suspensions, since LMPC circumvents the uncertainties resulting from the potentially heterogeneous behavior or inappropriate sampling from microplastic suspensions. Furthermore, LMPC could be advantageous for the generation of very accurate calibration series of spherical particles for microplastic analysis via pyrolysis-gas chromatography-mass spectrometry (down to 0.54 ng), as it omits the dissolution of bulk polymers.

Characteristic regional differences in trace element pattern of 2014 German North Sea surface Wadden sediments - A judge and assessment.

The European Marine Strategy Framework Directive (MSFD) requires good ecological status of the marine environment. This also includes the Wadden Sea located in the southeastern part of the North Sea and its chemical status of sediments. Based on results from campaigns conducted in the 1980s, 32 surface sediment samples were taken in 2014 to check whether the sampling strategy required for characterizing the trace element content in sediments is representative and to determine the degree of pollution and potential changes over the last decades. For this purpose the elemental mass fractions of 42 elements were assessed in the ≤20 µm grain size fraction of the surface sediments. Based on cluster analysis a clear correlation between the element distribution and the geographical location of the sampling locations of the German Wadden Sea could be found. As a result of the principal component analysis, three sub-catchments were significantly separated from each other by the characteristic element distributions in the sediments (Norderney and Weser, Elbe and offshore areas, and North Friesland). With the help of discriminant analysis, the classification was confirmed unambiguously. Small anomalies, such as potentially contaminated sites from WWII, could be identified. This proved that the sampling strategy for sediment characterization with reference to trace elements in the Wadden Sea of the German Bight is representative. The impact of regulation and changes on the overall sediment quality is most evident when looking at the environmentally critical elements such as As, Cd, Hg, and Cr. For these elements the mean mass fractions show a significant reduction over the last three decades. Current sediments feature only slightly elevated mass fractions of Ag, Cd, Ce, Cs, Nd, Pb and Se at some sampling locations.

Technology-critical elements in Rhine sediments - A case study on occurrence and spatial distribution.

Despite their presence in almost every technical device, little is known about the occurrence, distribution, and fate of technology-critical elements (TCEs) within the environment. Due to high economic demands and short product lifespans as well as low recycling rates, many TCEs appear to become emerging contaminants. Within the scope of this work, 57 sediment samples from the German part of the Rhine river, as well as various tributaries, were collected to study the occurrence and distribution of TCEs. This specific catchment area has consistently been subjected to strong anthropogenic influences over the last century. Hierarchical cluster analysis, as well as principal component analysis were used to gain first insights into the spatial distribution and possible sources of TCEs along the Rhine. Obtained mass fractions in conjunction with corresponding geoaccumulation indices (Igeo) provide first indications of a possible enrichment along the Rhine for the TCEs of interest (Ga, Ge, Nb, In, Te, rare earth elements, and Ta). Especially the mass fractions of Zn, Ge, In, La, Sm, and Gd exhibit significant anthropogenic inputs. For stations characterized by high Ge and In mass fractions, element fingerprints imply possible atmospheric deposition stemming from e.g. combustion processes. Distinct anomalies of La and Sm most likely originate from discharges located at the city of Worms into the Upper Rhine. Statistical analysis of all analyzed 55 elemental mass fractions revealed similar behavior of TCEs compared to classical heavy metals. Diffuse as well as point sources of TCEs are likely. As a result, this study provides further insight into the role of TCEs as potential emerging contaminants in the environment.

Spatial distribution of microplastics in the tropical Indian Ocean based on laser direct infrared imaging and microwave-assisted matrix digestion.

Suspended particulate matter was collected from subsurface (6 m) water along an E-W transect through the tropical Indian Ocean using a specialized inert (plastic free) fractionated filtration system. The samples were subjected to a new microwave-assisted "one-pot" matrix removal (efficiency: 94.3% ± 0.3% (1 SD, n = 3)) and microplastic extraction protocol (recovery: 95% ± 4%). The protocol enables a contamination-minimized digestion and requires only four filtration steps. In comparison, classical sample processing approaches involve up to eight filtration steps until the final analysis. Microplastics were identified and physically characterized by means of a novel quantum cascade laser-based imaging routine. LDIR imaging facilitates the analysis of up to 1000 particles/fibers (<300 µm) within approximately 1-2 h. In comparison to FTIR and Raman imaging, it can help to circumvent uncertainties, e. g. from subsampling strategies due to long analysis and post-processing times of large datasets. Over 97% of all particles were correctly identified by the automated routine - without spectral reassignments. Moreover, 100% agreement was obtained between ATR-FTIR and LDIR-based analysis regarding particles and fibers >300 µm. The mean microplastic concentration of the analyzed samples was 50 ± 30 particles/fibers m-3 (1 SD, n = 21). Number concentrations ranged from 8 to 132 particles/fibers m-3 (20-300 µm). The most abundant polymer clusters were acrylates/polyurethane/varnish (49%), polyethylene terephthalate (26%), polypropylene (8%), polyethylene (4%) and ethylene-vinyl acetate (4%). 96% of the microplastic particles had a diameter <100 µm. Though inter-study comparison is difficult, the investigated area exhibits a high contamination with particulate plastics compared to other open ocean regions. A distinct spatial trend was observed with an increasing share of the size class 20-50 µm from east to west.

Occurrence and Temporal Variation of Technology-Critical Elements in North Sea Sediments-A Determination of Preliminary Reference Values.

As interest in the investigation of possible sources and environmental sinks of technology-critical elements (TCEs) continues to grow, the demand for reliable background level information of these elements in environmental matrices increases. In this study, a time series of ten years of sediment samples from two different regions of the German North Sea were analyzed for their mass fractions of Ga, Ge, Nb, In, REEs, and Ta (grain size fraction < 20 µm). Possible regional differences were investigated in order to determine preliminary reference values for these regions. Throughout the investigated time period, only minor variations in the mass fractions were observed and both regions did not show significant differences. Calculated local enrichment factors ranging from 0.6 to 2.3 for all TCEs indicate no or little pollution in the investigated areas. Consequently, reference values were calculated using two different approaches (Median + 2 median absolute deviation (M2MAD) and Tukey inner fence (TIF)). Both approaches resulted in consistent threshold values for the respective regions ranging from 158 µg kg-1 for In to 114 mg kg-1 for Ce. As none of the threshold values exceed the observed natural variation of TCEs in marine and freshwater sediments, they may be considered baseline values of the German Bight for future studies.

Calcification-driven CO2 emissions exceed "Blue Carbon" sequestration in a carbonate seagrass meadow.

Long-term "Blue Carbon" burial in seagrass meadows is complicated by other carbon and alkalinity exchanges that shape net carbon sequestration. We measured a suite of such processes, including denitrification, sulfur, and inorganic carbon cycling, and assessed their impact on air-water CO2 exchange in a typical seagrass meadow underlain by carbonate sediments. Eddy covariance measurements reveal a consistent source of CO2 to the atmosphere at an average rate of 610 ± 990 µmol m−2 hour−1 during our study and 700 ± 660 µmol m−2 hour−1 (6.1 mol m−2 year−1) over an annual cycle. Net alkalinity consumption by ecosystem calcification explains >95% of the observed CO2 emissions, far exceeding organic carbon burial and anaerobic alkalinity generation. We argue that the net carbon sequestration potential of seagrass meadows may be overestimated if calcification-induced CO2 emissions are not accounted for, especially in regions where calcification rates exceed net primary production and burial.

Using Sr-Nd-Pb isotope systems to trace sources of sediment and trace metals to the Weser River system (Germany) and assessment of input to the North Sea.

In order to trace the sources of sediment materials and trace metals in the Weser River system (Germany), and the riverine input to the North Sea, Sr, Nd and Pb isotopes, together with multi-elemental compositions, were measured for sediments collected over the entire Weser River Basin, from headwaters to the estuary. Mass fractions of metals, including Ag, Cd, and Pb, and of one metalloid, Sb, higher than their crustal abundance, were observed within the entire Weser Basin. Isotope-amount ratio n(87Sr)/n(86Sr) and εNd ranged from 0.71182 ± 0.00005 to 0.72880 ± 0.00009 and -11.3 ± 0.3 to -21.0 ± 0.3, respectively. n(206Pb)/n(204Pb), n(207Pb)/n(204Pb), and n(208Pb)/n(204Pb) ranged from 18.226 ± 0.008 to 18.703 ± 0.012, 15.613 ± 0.007 to 15.653 ± 0.012 and 38.14 ± 0.02 to 38.84 ± 0.02, respectively. Sr and Nd isotope compositions reflected primarily a mixture of natural materials derived from the Weser Basin. Pb isotope signatures indicated strong anthropogenic influences in the middle-lower Weser region. Pb isotopic compositions in the sediments from the Aller (tributary of the Weser) and its tributary suggested influence from historical Pb-Zn ore mining in the Harz Mountains that might contribute to the observed elevated mass fractions of Ag, Cd, Sb and Pb in that region. K-means cluster and principal component analysis of the Sr, Nd, and Pb isotope data yielded results consistent with their isotope systematics, supporting statistical analysis as an unsupervised tool in isotope fingerprinting studies. Sr, Nd, and Pb isotopic signatures in the sediments of the Weser were distinctively different from those of another major river discharging into the North Sea, the Elbe. This suggested that this Sr, Nd, and Pb isotope dataset can be used to distinguish riverine input of sediment materials and metals between the two rivers, thereby assessing their individual contribution to materials transported into the North Sea.

Comparison and uncertainty evaluation of two centrifugal separators for microplastic sampling.

For commonly applied microplastic sampling approaches based on filtration, high throughput and no size-discrimination are conflicting goals. Therefore, we propose two efficient centrifugal separators for small microplastic sampling, namely the utilization of a hydrocyclone as well as a continuous flow centrifuge. Thorough method optimization was followed by application in an extensive sampling study to investigate the separators' retention behavior for particulate plastics from estuarine waters. Microplastic concentrations ranged from 193 to 2072 particles m-3. The most dominant identified polymer types were polypropylene, acrylates, polyvinyl chloride and polyethylene. More than 95% of particles were < 100 µm. For the first time in microplastic research, an expanded uncertainty was calculated according to the "Guide to the expression of Uncertainty in Measurement" (JCGM 100:2008). Bottom-up uncertainty evaluation revealed the different sampling methods (~ 44%), sample replicates (~ 26%) and the different detection techniques (~ 16%) as the major sources of uncertainty. Depending on the number of particles detected in the samples, the relative expanded uncertainty (Urel (k = 2)) ranged from 24% up to > 200% underpinning tremendous importance of sound uncertainty evaluation. Our results indicate that scientist should rethink many "observed patterns" in the literature due to being insignificant and herewith not real.

Quantitative speciation of volatile sulphur compounds from human cadavers by GC-ICP-MS.

This work demonstrates the first forensic application of GC-ICP-MS for improved investigations of volatile organic compounds originating from a decomposing body. Volatile organic compounds were extracted from the headspace of human remains using sorbent tubes over a total time of 39 days. To account for naturally abundant species, control sites were prepared and sampled accordingly. All samples were spiked with an internal standard to minimise drift effects and errors during sample preparation and further analysis. Compound independent quantification was possible from a single chromatogram with a standard mix containing volatile pesticide compounds representing different mass fractions of target elements for calibration. Phosphorus, sulphur and chlorine were investigated as biologically relevant elements, which potentially form detectable volatile species during decomposition. The limits of detection of these elements in the headspace were 0.7, 5.4 and 1.6 ng/L, respectively. For sulphur, we identified abundant species which increased in concentrations of up to 1310 ng/L in the headspace above the remains. The concentrations were time dependent and show potential as forensic markers to determine post-mortem intervals or decomposition states. The universal quantification, standardisation and the high sensitivity of GC-ICP-MS augments traditional GC-MS analyses.

Substituting HF by HBF4- an optimized digestion method for multi-elemental sediment analysis via ICP-MS/MS.

Determination of elemental mass fractions in sediments plays a major role in evaluating the environmental status of aquatic ecosystems. Herewith, the optimization of a new total digestion protocol and the subsequent analysis of 48 elements in different sediment reference materials (NIST SRM 2702, GBW 07313, GBW 07311 and JMC-2) based on ICP-MS/MS detection is presented. The developed method applies microwave acid digestion and utilizes HBF4 as fluoride source for silicate decomposition. Similar to established protocols based on HF, HBF4 ensures the dissolution of the silicate matrix, as well as other refractory oxides. As HBF4 is not acutely toxic; no special precautions have to be made and digests can be directly measured via ICP-MS without specific sample inlet systems, evaporation steps or the addition of e.g. H3BO3, in order to mask excess HF. Different acid mixtures with and without HBF4 were evaluated in terms of digestion efficiency based on the trace metal recovery. The optimized protocol (5 mL HNO3, 2 mL HCL, 1 mL HBF4) allows a complete dissolution of the analyzed reference materials, as well as quantitative recoveries for a wide variety of certified analytes. Low recoveries for e.g. Sr, Ba and rare earth elements due to fluoride precipitation of HF-based digestions protocols, can be avoided by the usage of HBF4 instead. Based on the usage of high purity HBF4 all relevant trace, as well as matrix elements can be analyzed with sufficiently low LOQs (0.002 µg L-1 for U up to 6.7 µg L-1 for Al). In total, 34 elements were within a recovery range of 80%-120% for all three analyzed reference materials GBW 07313, GBW 07311 and JMC-2. 14 elements were outside a recovery range of 80%-120% for at least one of the analyzed reference materials.

A metrologically traceable protocol for the quantification of trace metals in different types of microplastic.

The presence of microplastic (MP) particles in aquatic environments raised concern about possible enrichment of organic and inorganic pollutants due to their specific surface and chemical properties. In particular the role of metals within this context is still poorly understood. Therefore, the aim of this work was to develop a fully validated acid digestion protocol for metal analysis in different polymers, which is a prerequisite to study such interactions. The proposed digestion protocol was validated using six different certified reference materials in the microplastic size range consisting of polyethylene, polypropylene, acrylonitrile butadiene styrene and polyvinyl chloride. As ICP-MS/MS enabled time-efficient, sensitive and robust analysis of 56 metals in one measurement, the method was suitable to provide mass fractions for a multitude of other elements beside the certified ones (As, Cd, Cr, Hg, Pb, Sb, Sn and Zn). Three different microwaves, different acid mixtures as well as different temperatures in combination with different hold times were tested for optimization purposes. With the exception of Cr in acrylonitrile butadiene styrene, recovery rates obtained using the optimized protocol for all six certified reference materials fell within a range from 95.9% ± 2.7% to 112% ± 7%. Subsequent optimization further enhanced both precision and recoveries ranging from 103% ± 5% to 107 ± 4% (U; k = 2 (n = 3)) for all certified metals (incl. Cr) in acrylonitrile butadiene styrene. The results clearly show the analytical challenges that come along with metal analysis in chemically resistant plastics. Addressing specific analysis tools for different sorption scenarios and processes as well as the underlying kinetics was beyond this study's scope. However, the future application of the two recommended thoroughly validated total acid digestion protocols as a first step in the direction of harmonization of metal analysis in/on MP will enhance the significance and comparability of the generated data. It will contribute to a better understanding of the role of MP as vector for trace metals in the environment.

Characterization of alloying components in galvanic anodes as potential environmental tracers for heavy metal emissions from offshore wind structures.

The impact of offshore constructions on the marine environment is unknown in many aspects. The application of Al- and Zn-based galvanic anodes as corrosion protection results in the continuous emission of inorganic matter (e.g. >80 kg Al-anode material per monopile foundation and year) into the marine environment. To identify tracers for emissions from offshore wind structures, anode materials (Al-based and Zn-based) were characterized for their elemental and isotopic composition. An acid digestion and analysis method for Al and Zn alloys was adapted and validated using the alloy CRMs ERM®-EB317 (AlZn6CuMgZr) and ERM®-EB602 (ZnAl4Cu1). Digests were measured for their elemental composition by ICP-MS/MS and for their Pb isotope ratios by MC ICP-MS. Ga and In were identified as potential tracers. Moreover, a combined tracer approach of the elements Al, Zn, Ga, Cd, In and Pb together with Pb isotope ratios is suggested for a reliable identification of offshore-wind-farm-induced emissions. In the Al anodes, the mass fractions were found to be >94.4% of Al, >26200 mg kg-1 of Zn, >78.5 mg kg-1 of Ga, >0.255 mg kg-1 of Cd, >143 mg kg-1 of In and >6.7 mg kg-1 of Pb. The Zn anodes showed mass fractions of >2160 mg kg-1 of Al, >94.5% of Zn, >1.31 mg kg-1 of Ga, >254 mg kg-1 of Cd, >0.019 mg kg-1 of In and >14.1 mg kg-1 of Pb. The n(208Pb)/n(206Pb) isotope ratios in Al anodes range from 2.0619 to 2.0723, whereas Zn anodes feature n(208Pb)/n(206Pb) isotope ratios ranging from 2.0927 to 2.1263.

Extreme spatial variation of Sr, Nd and Pb isotopic signatures and 48 element mass fractions in surface sediment of the Elbe River Estuary - Suitable tracers for processes in dynamic environments?

The Elbe River has been long considered as one of the most anthropogenically impacted rivers in Europe. Its estuary is characterized by strong tidal effects, continuous dredging and dumping of sediment, and intense ship traffic between the North Sea and the Port of Hamburg. The aim of this study was to elucidate if a combined multi-element fingerprinting and isotopic tracer approach represented a suitable tool to investigate transport and mixing processes of inorganic contaminants within a complex and highly dynamic estuarine environment. A total of 37 surface sediment samples from the tidal Elbe were characterized in a comprehensive survey by determining the mass fractions of 48 elements and the isotopic signatures of stable Sr, Nd and Pb. Statistical data analysis resolved four discrete clusters of sampling locations in the estuary: One cluster upstream of the city of Hamburg, two clusters within the mixing zone between Hamburg and the mouth of the Elbe Estuary and one cluster in the mouth of the Estuary. River sediment entering the estuary carry significantly higher loads of metals (e.g. Cu, Zn, Sb, Cd and Pb), which are rapidly "diluted" by lower elemental mass fractions in marine sediment on a remarkably small regional scale. The cluster within the mouth of the estuary is mainly characterized by extreme isotopic variations of n(208Pb)/n(204Pb) ranging from 38.67 ±â€¯0.15 to 73.86 ±â€¯0.29, beside high mass fractions of U, Th, and some rare-earth elements. Determined Pb isotope ratios are among the highest reported values for terrestrial materials. This study indicates the general potential of combined element fingerprinting and isotope tracer approaches to elucidate processes in complex river systems. Furthermore, it represents an initial characterization of the catchment area of the Elbe River as basis for future studies on river and harbor management.

Quantitative and Qualitative Analysis of Three Classes of Sulfur Compounds in Crude Oil.

Owing to the environmental hazards arising from sulfur-containing combustion products, strong legal regulations exist to reduce the sulfur content of transportation fuels down to a few ppm. With the ongoing depletion of low-sulfur crude oil reservoirs, increased technological efforts are needed for crude oil refining to meet these requirements. The desulfurization step is a critical part of the refining process but partly suffers from the recalcitrance of certain species to sulfur removal and the inability to quantitatively understand the behavior of individual compound classes during the process. We herein present a new and simple approach for the parallel quantification of three different classes of sulfur species present in crude oils by LC separation and on-line detection and quantification by ICP-MS/MS. This approach will help to estimate the amount of recalcitrant species and thus facilitate the optimization of desulfurization conditions during fuel production.

The performance of single and multi-collector ICP-MS instruments for fast and reliable 34S/32S isotope ratio measurements.

The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3-0.5% (uc,rel), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement uc,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%).