Quantitative pulsatility measurements using 3D dynamic ultrasound localization microscopy.

A rise in blood flow velocity variations (i.e. pulsatility) in the brain, caused by the stiffening of upstream arteries, is associated with cognitive impairment and neurodegenerative diseases. The study of this phenomenon requires brain-wide pulsatility measurements, with large penetration depth and high spatiotemporal resolution. The development of dynamic ultrasound localization microscopy (DULM), based on ULM, has enabled pulsatility measurements in the rodent brain in 2D. However, 2D imaging accesses only one slice of the brain and measures only 2D-projected and hence biased velocities . Herein, we present 3D DULM: using a single ultrasound scanner at high frame rate (1000-2000 Hz), this method can produce dynamic maps of microbubbles flowing in the bloodstream and extract quantitative pulsatility measurements in the cat brain with craniotomy and in the mouse brain through the skull, showing a wide range of flow hemodynamics in both large and small vessels. We highlighted a decrease in pulsatility along the vascular tree in the cat brain, which could be mapped with ultrasound down to a few tens of micrometers for the first time. We also performed an intra-animal validation of the method by showing consistent measurements between the two sides of the Willis circle in the mouse brain. Our study provides the first step towards a new biomarker that would allow the detection of dynamic abnormalities in microvessels in the brain, which could be linked to early signs of neurodegenerative diseases.

Phase Aberration Correction for In Vivo Ultrasound Localization Microscopy Using a Spatiotemporal Complex-Valued Neural Network.

Ultrasound Localization Microscopy (ULM) can map microvessels at a resolution of a few micrometers ( [Formula: see text]). Transcranial ULM remains challenging in presence of aberrations caused by the skull, which lead to localization errors. Herein, we propose a deep learning approach based on recently introduced complex-valued convolutional neural networks (CV-CNNs) to retrieve the aberration function, which can then be used to form enhanced images using standard delay-and-sum beamforming. CV-CNNs were selected as they can apply time delays through multiplication with in-phase quadrature input data. Predicting the aberration function rather than corrected images also confers enhanced explainability to the network. In addition, 3D spatiotemporal convolutions were used for the network to leverage entire microbubble tracks. For training and validation, we used an anatomically and hemodynamically realistic mouse brain microvascular network model to simulate the flow of microbubbles in presence of aberration. The proposed CV-CNN performance was compared to the coherence-based method by using microbubble tracks. We then confirmed the capability of the proposed network to generalize to transcranial in vivo data in the mouse brain (n=3). Vascular reconstructions using a locally predicted aberration function included additional and sharper vessels. The CV-CNN was more robust than the coherence-based method and could perform aberration correction in a 6-month-old mouse. After correction, we measured a resolution of [Formula: see text] for younger mice, representing an improvement of 25.8%, while the resolution was improved by 13.9% for the 6-month-old mouse. This work leads to different applications for complex-valued convolutions in biomedical imaging and strategies to perform transcranial ULM.

Mercury distribution, mobilization and bioavailability in polluted sediments of Scheldt Estuary and Belgian Coastal Zone.

In this study, the vertical distribution of mercury (Hg) in estuarine and marine sediment porewaters and solid phases was assessed by conventional and passive sampling techniques in the historically polluted Scheldt Estuary and Belgian Coastal Zone (BCZ). The Diffusive Gradients in Thin-films (DGT) measured labile Hg concentrations (HgLA) were mostly lower than the porewater Hg concentrations (HgPW), and they also presented different vertical distribution patterns. Still high Hg concentrations in the sediment solid phases, comparable to the historical ones, were observed. Even though pH, redox potential and dissolved sulfide concentration could influence the Hg biogeochemical behaviour, organic matter (OM) played a key role in governing Hg mobilization from sediment solid phase to porewater and in its partitioning between porewater and solid phase over depth. In the marine sediments, where OM had a marine signature, higher labile Hg concentrations in the porewater and faster resupply from the solid phase were observed. The DGT technique showed significant potential not only for the measurement of bioavailable Hg fractions in porewater, but also for the assessment of kinetic parameters governing the release of labile Hg species from the solid phase with the assistance of the DGT Induced Fluxes in Sediments (DIFS) model.

Investigation on metal geochemical cycling in an anthropogenically impacted tidal river in Belgium.

The geochemical behavior of metals in water and sediment was investigated in the tidal section of the Zenne River in Belgium. Twelve-hour sampling campaigns were performed in October 2013 and March 2021 at the mouth of the Zenne River, under dry and rainy weather conditions respectively. Water samples were collected every hour while the passive samplers of Diffusive Gradients in Thin-films (DGT) were deployed continuously during a tidal cycle. In addition, bottom sediments were sampled at the tidal station and water samples were taken upstream and downstream of that station to identify the metal sources. The highest concentrations of Fe, Mn, Pb, Cr, Ni and Zn appear at low tide, indicating the Zenner River as a main source. However, for Co, Cd and Cu, other sources including upstream transport may explain their behavior during a tidal cycle. Fe, Pb and Cr are essentially transported in the particulate phase (<10 % dissolved) while the other metals in the dissolved phase (20 to 90 %). Rainfall and wind gust events also play an important role in trace metal distribution, increasing sediment resuspension and metal desorption. A good agreement was found between the time-averaged dissolved and DGT-labile metal concentrations with the exception of Cu and Fe, which form strong organic Cu complexes and Fe colloids respectively. The sediments of the tidal Zenne are contaminated by trace metals, thus acting as a secondary pollution source to the river. The reductive dissolution of Mn and Fe oxyhydroxides and the release of associated trace metals are the main mobilization mechanisms. Knowledge of the upstream and downstream levels in the water column, the benthic fluxes, which are based on turbulent diffusion, and the partitioning between dissolved and particulate phases allow to explain the metal concentration variations during the tidal cycle.

Origin and partitioning of mercury in the polluted Scheldt Estuary and adjacent coastal zone.

Estuaries and coastal zones are areas with complex biogeochemical and hydrological cycles and are generally facing intense pollution due to anthropogenic activities. An emblematic example is the Scheldt Estuary which ends up in the North Sea and has been historically heavily contaminated by multiple pollutants, including mercury (Hg). We report here Hg species and their levels in surface waters of the Scheldt Estuary and the Belgian Part of North Sea (BPNS) from different sampling campaigns in February-April 2020 and 2021. Along the estuary, Hg concentration on suspended particles ([HgSPM]) progressively decreased with increasing salinity and was strongly correlated with organic matter content (%Corg) and origin (identified with δ13Corg). While [HgSPM] drives total Hg concentration in the estuary (total dissolved Hg, HgTD is only 7 ± 6 %), annual and daily variations of total Hg levels were mostly attributed to changes in SPM loads depending on river discharge and tidal regime. In the BPNS, a significant fraction of total Hg occurs as HgTD (40 ± 21 %) and the majority of this HgTD was reducible (i.e. labile Hg), meaning potentially available for microorganisms. Compared to the '90s, a significant decrease of [HgSPM] was observed in the estuary, but this was not the case for [HgTD], which can be due to (1) still significant discrete discharges from Antwerp industrial area, and (2) higher Hg partitioning towards the dissolved phase in the water column relative to the '90s. Our results highlight the important contribution of the Scheldt estuary for the Hg budget in North Sea coastal waters, as well as the need for seasonal monitoring of all Hg species.

A multimethodological evaluation of arsenic in the Zenne River, Belgium: Sources, distribution, geochemistry, and bioavailability.

The distribution and geochemistry of arsenic (As) in water and sediments of the Zenne River, a small urban river flowing through Brussels (Belgium), were assessed based on the results of 18 sampling campaigns performed between 2010 and 2021. In general, concentrations of As sharply increase between Vilvoorde and Eppegem and are up to 6-8 times higher in the section downstream of Eppegem in comparison to the upstream part of the Zenne. The monitoring surveys in which the grab water samples were taken at a 1-hour sampling frequency revealed that the large temporal variability in As concentrations found in the downstream part of the river is driven by the tidal cycle. The diffusive gradients in thin films (DGT) technique was used to assess the DGT labile As species in surface water and sediment porewater. Three DGT sorbents (Metsorb, Lewatit FO 36, and ZrO2) for the determination of total As were applied to compare their performance, and the 3-mercaptopropyl-functionalized silica (3-MFS) was used for the speciation of As(III) in porewater. Arsenic species are fully labile in surface waters as the DGT time-integrated concentrations of As were in good agreement with the average concentrations calculated from the grab samplings. In sediment porewaters, As is predominantly present as non-DGT labile species (66-93 %), and the DGT labile As fraction is dominated by As(III). Flux calculations evaluating the relative importance of different As sources to the Zenne River revealed the presence of a point source on the tributary Tangebeek, which contributes to 87 % of the As load carried by the Zenne River.

Piezoelectric Micromachined Ultrasonic Transducer for Arterial Wall Dynamics Monitoring.

In this article, a [Formula: see text] piezoelectric micromachined ultrasonic transducer (PMUT) array is designed and driven with one cycle of a 5-MHz sinusoid at 10 [Formula: see text] for radial artery motion tracking. The transmit and receive performance figure of merit (FOM) of an individual PMUT over operating frequency is modeled and validated using laser Doppler vibrometer (LDV) measurements. Given a fixed cross section, the FOM inversely scales with frequency. The array aperture size is selected to obtain enough pressure and received signal to measure the radial artery wall reflection at a 5-mm depth in tissue. The 2-mm acoustic beamwidth provides enough lateral resolution for radial artery wall motion tracking. Single-line ultrasonic pulse-echo measurements with high time resolution, also called M-mode ultrasound imaging, are demonstrated to reproduce a known target motion profile with a precision of around 0.5 [Formula: see text]. In vivo radial artery dynamics are measured by placing the sensor on the wrist of a volunteer. The measured diameter change waveform of the radial artery is consistent with reports in the literature and captures key arterial pulse waveform features, including systolic upstroke, systolic decline, dicrotic notch, and diastolic runoff. The system has sufficient accuracy and precision to measure both the 50 [Formula: see text] overall diameter change and the 5- [Formula: see text] diameter change due to the dicrotic notch. A heart rate of 70 beats/min is also derived. This demonstrates the great potential of custom PMUT arrays for continuous cardiovascular system monitoring.

Equivalent time active cavitation imaging.

Rationale. Despite the development of a large number of neurologically active drugs, brain diseases are difficult to treat due to the inability of many drugs to penetrate the blood-brain barrier. High-intensity focused ultrasound (HIFU) blood-brain barrier opening in a site-specific manner could significantly expand the spectrum of available drug treatments. However, without monitoring, brain damage and off-target effects can occur during these treatments. While some methods can monitor inertial cavitation, temperature increase, or passively monitor cavitation events, to the best of our knowledge none of them can actively and spatiotemporally map the HIFU pressure field during treatment.Methods. Here we detail the development of a novel ultrasound imaging modality called equivalent time active cavitation imaging (ETACI) capable of characterizing the HIFU pressure field through stable cavitation events across the field of view with an ultrafast active imaging setup. This work introduces (1) a novel plane wave sequence whose transmit delays increase linearly with transmit events enabling the sampling of high-frequency cavitation events, and (2) an algorithm allowing the processing of the microbubble signal for pressure field mapping. The pressure measurements with our modality were first carried outin vitrofor hydrophone comparison and thenin vivoduring blood-brain barrier opening treatment in mice.Results. This study demonstrates the capability of ETACI to spatiotemporally characterize a modulation pressure field with an active imaging setup. The resulting pressure field mapping reveals a good correlation with hydrophone measurements. Further results iareprovided experimentallyin vivowith promising results.Conclusion. This proof of concept establishes the first steps towards a novel ultrasound modality for monitoring focused ultrasound blood-brain barrier opening, allowing new possibilities for a safe and precise monitoring method.

Translation of Simultaneous Vessel Wall Motion and Vectorial Blood Flow Imaging in Healthy and Diseased Carotids to the Clinic: A Pilot Study.

This study aims to investigate the clinical feasibility of simultaneous extraction of vessel wall motion and vectorial blood flow at high frame rates for both extraction of clinical markers and visual inspection. If available in the clinic, such a technique would allow a better estimation of plaque vulnerability and improved evaluation of the overall arterial health of patients. In this study, both healthy volunteers and patients were recruited and scanned using a planewave acquisition scheme that provided a data set of 43 carotid recordings in total. The vessel wall motion was extracted based on the complex autocorrelation of the signals received, while the vector flow was extracted using the transverse oscillation technique. Wall motion and vector flow were extracted at high frame rates, which allowed for a visual appreciation of tissue movement and blood flow simultaneously. Several clinical markers were extracted, and visual inspections of the wall motion and flow were conducted. From all the potential markers, young healthy volunteers had smaller artery diameter (7.72 mm) compared with diseased patients (9.56 mm) ( p -value ≤ 0.001), 66% of diseased patients had backflow compared with less than 10% for the other patients ( p -value ≤ 0.05), a carotid with a pulse wave velocity extracted from the wall velocity greater than 7 m/s was always a diseased vessel, and the peak wall shear rate decreased as the risk increases. Based on both the pathological markers and the visual inspection of tissue motion and vector flow, we conclude that the clinical feasibility of this approach is demonstrated. Larger and more disease-specific studies using such an approach will lead to better understanding and evaluation of vessels, which can translate to future use in the clinic.

Tapered Vector Doppler for Improved Quantification of Low Velocity Blood Flow.

A new vector velocity estimation scheme is developed, termed tapered vector Doppler (TVD), aiming to improve the accuracy of low velocity flow estimation. This is done by assessing the effects of singular value decomposition (SVD) and finite impulse response (FIR) filters and designing an estimator which accounts for signal loss due to filtering. Synthetic data created using a combination of in vivo recordings and flow simulations were used to investigate scenarios with low blood flow, in combination with true clutter motion. Using this approach, the accuracy and precision of TVD was investigated for a range of clutter-to-blood and signal-to-noise ratios. The results indicated that for the investigated carotid application and setup, the SVD filter performed as a frequency-based filter. For both SVD and FIR filters, suppression of the clutter signal resulted in large bias and variance in the estimated blood velocity magnitude and direction close to the vessel walls. Application of the proposed tapering technique yielded significant improvement in the accuracy and precision of near-wall vector velocity measurements, compared to non-TVD and weighted least squares approaches. In synthetic data, for a blood SNR of 5 dB, and in a near-wall region where the average blood velocity was 9 cm/s, the use of tapering reduced the average velocity magnitude bias from 26.3 to 1.4 cm/s. Complex flow in a carotid bifurcation was used to demonstrate the in vivo performance of TVD, and it was shown that tapering enables vector velocity estimation less affected by clutter and clutter filtering than what could be obtained by adaptive filter design only.

So you think you can DAS? A viewpoint on delay-and-sum beamforming.

Delay-and-sum (DAS) is the most widespread digital beamformer in high-frame-rate ultrasound imaging. Its implementation is simple and compatible with real-time applications. In this viewpoint article, we describe the fundamentals of DAS beamforming. The underlying theory and numerical approach are detailed so that users can be aware of its functioning and limitations. In particular, we discuss the importance of the f-number and speed of sound on image quality, and propose one solution to set their values from a physical viewpoint. We suggest determining the f-number from the directivity of the transducer elements and the speed of sound from the phase dispersion of the delayed signals. Simplified Matlab codes are provided for the sake of clarity and openness. The effect of the f-number and speed of sound on the lateral resolution and contrast-to-noise ratio was investigated in vitro and in vivo. If not properly preset, these two factors had a substantial negative impact on standard metrics of image quality (namely CNR and FWHM). When beamforming with DAS in vitro or in vivo, it is recommended to optimize these parameters in order to use it wisely and prevent image degradation.

Mercury bioaccumulation in tilefish from the northeastern Gulf of Mexico 2 years after the Deepwater Horizon oil spill: Insights from Hg, C, N and S stable isotopes.

Mercury (Hg) concentration in fish of the Gulf of the Mexico (GoM) is a major concern due to the importance of the GoM for U.S. fisheries. The Deepwater Horizon (DWH) oil spill in April 2010 in the northern GoM resulted in large amounts of oil and dispersant released to the water column, which potentially modified Hg bioaccumulation patterns in affected areas. We measured Hg species (methylmercury (MMHg) and inorganic Hg (IHg)) concentrations, and light (C, N and S) and Hg stable isotopes in muscle and liver tissues from tilefish (Lopholatilus chamaleonticeps) sampled in 2012 and 2013 along the shelf break of the northeastern GoM. Fish located close to the mouth of the Mississippi River (MR) and northwest of the DWH well-head (47 km) showed significantly lower Hg levels in muscle and liver than fish located further northeast of the DWH (>109 km), where 98% of tilefish had Hg levels in the muscle above US consumption advisory thresholds (50% for tilefish close to the DWH). Differences in light and Hg stable isotopes signatures were observed between these two areas, showing higher δ15N, and lower δ202Hg, Δ199Hg and δ34S in fish close to the DWH/MR. This suggests that suspended particles from the MR reduces Hg bioavailability at the base of the GoM food chains. This phenomenon can be locally enhanced by the DWH that resulted in increased particles in the water column as evidenced by the marine snow layer in the sediments. On the other hand, freshly deposited Hg associated with organic matter in more oligotrophic marine waters enhanced Hg bioaccumulation in local food webs. Comparing Hg isotopic composition in liver and muscle of fish indicates specific metabolic response in fish having accumulated high levels of MMHg.

Video Magnification Applied in Ultrasound.

GOAL: This paper describes a method to enhance, visualize, and reveal subtle motion that can be present in medical images. As proposed in vision applications, the principle is to magnify displacement applied, in this case, to cardiovascular tissues (carotid). METHODS: In the example presented, ultrasound data were acquired at a high frame rate and two-dimensional motion was estimated, amplified, and reapplied in ultrasound carotid sequences. RESULTS: Video magnification makes fast and complex phenomena of human tissue visible. In fact, not only pulse and reflected wave, but also global radial and longitudinal motion in the example presented are visible with video magnification. CONCLUSION: Video magnification can be used in medical imaging for subtle motion visualization. One of the many possible applications is direct visualization of a local modification in terms of stiffness of a tissue (due to local necrosis, for instance) from acquisition. Moreover, video magnification can be executed with any type of imaging modality. SIGNIFICANCE: Video magnification could be a new tool for physicians to highlight new pathology indicators or for long-term disease monitoring.

Sources and fate of mercury pollution in Almadén mining district (Spain): Evidences from mercury isotopic compositions in sediments and lichens.

Variations in mercury (Hg) isotopic compositions have been scarcely investigated until now in the Almadén mining district (Spain), which is one of the most impacted Hg areas worldwide. In this work, we explore and compare Hg isotopic signatures in sediments and lichens from Almadén mining district and its surroundings in order to identify and trace Hg aquatic and atmospheric contamination sources. No statistically significant mass independent fractionation was observed in sediments, while negative Δ(201)Hg values from -0.12 to -0.21‰ (2SD = 0.06‰) were found in lichens. A large range of δ(202)Hg values were reported in sediments, from -1.86 ± 0.21‰ in La Serena Reservoir sites far away from the pollution sources to δ(202)Hg values close to zero in sediments directly influenced by Almadén mining district, whereas lichens presented δ(202)Hg values from -1.95 to -0.40‰ (2SD = 0.15‰). A dilution or mixing trend in Hg isotope signatures versus the distance to the mine was found in sediments along the Valdeazogues River-La Serena Reservoir system and in lichens. This suggests that Hg isotope fingerprints in these samples are providing a direct assessment of Hg inputs and exposure from the mining district, and potential information on diffuse atmospheric contamination and/or geochemical alteration processes in less contaminated sites over the entire hydrosystem. This study confirms the applicability of Hg isotope signatures in lichens and sediments as an effective and complementary tool for tracing aquatic and atmospheric Hg contamination sources and a better constraint of the spatial and temporal fate of Hg released by recent or ancient mining activities.

Natural Hg isotopic composition of different Hg compounds in mammal tissues as a proxy for in vivo breakdown of toxic methylmercury.

In the last decade, specific attention has been paid to total mercury (HgT) stable isotopic composition, especially in natural samples such as aquatic organisms, due to its potential to track the cycle of this toxic element in the environment. Here, we investigated Hg Compound Specific stable Isotopic Composition (CSIC) of natural inorganic Hg (iHg) and methylmercury (MMHg) in various tissues of aquatic mammals (Beluga whale from the Arctic marine environment and seals from the freshwater lake Baikal, Russia). In seals' organs the variation in mass dependent fractionation (MDF, δ(202)Hg) for total Hg was significantly correlated to the respective fraction of iHg and MMHg compounds, with MMHg being enriched by ∼ 3‰ in heavier isotopes relative to iHg. On the other hand, we observe insignificant variation in Hg mass independent isotope fractionation (MIF, Δ(199)Hg) among iHg and MMHg in all organs for the same mammal species and MMHg in prey items. MIF signatures suggest that both MMHg and iHg in aquatic mammals have the same origin (i.e., MMHg from food), and are representative of Hg photochemistry in the water column of the mammal ecosystem. MDF signatures of Hg compounds indicate that MMHg is demethylated in vivo before being stored in the muscle, and the iHg formed is stored in the liver, and to a lesser extent in the kidney, before excretion. Thus, Hg CSIC analysis in mammals can be a powerful tool for tracing the metabolic response to Hg exposure.

Hg Stable Isotope Time Trend in Ringed Seals Registers Decreasing Sea Ice Cover in the Alaskan Arctic.

Decadal time trends of mercury (Hg) concentrations in Arctic biota suggest that anthropogenic Hg is not the single dominant factor modulating Hg exposure to Arctic wildlife. Here, we present Hg speciation (monomethyl-Hg) and stable isotopic composition (C, N, Hg) of 53 Alaskan ringed seal liver samples covering a period of 14 years (1988-2002). In vivo metabolic effects and foraging ecology explain most of the observed 1.6 ‰ variation in liver δ(202)Hg, but not Δ(199)Hg. Ringed seal habitat use and migration were the most likely factors explaining Δ(199)Hg variations. Average Δ(199)Hg in ringed seal liver samples from Barrow increased significantly from +0.38 ± 0.08‰ (±SE, n = 5) in 1988 to +0.59 ± 0.07‰ (±SE, n = 7) in 2002 (4.1 ± 1.2% per year, p < 0.001). Δ(199)Hg in marine biological tissues is thought to reflect marine Hg photochemistry before biouptake and bioaccumulation. A spatiotemporal analysis of sea ice cover that accounts for the habitat of ringed seals suggests that the observed increase in Δ(199)Hg may have been caused by the progressive summer sea ice disappearance between 1988 and 2002. While changes in seal liver Δ(199)Hg values suggests a mild sea ice control on marine MMHg breakdown, the effect is not large enough to induce measurable HgT changes in biota. This suggests that Hg trends in biota in the context of a warming Arctic are likely controlled by other processes.

Identical Hg isotope mass dependent fractionation signature during methylation by sulfate-reducing bacteria in sulfate and sulfate-free environment.

Inorganic mercury (iHg) methylation in aquatic environments is the first step leading to monomethylmercury (MMHg) bioaccumulation in food webs and might play a role in the Hg isotopic composition measured in sediments and organisms. Methylation by sulfate reducing bacteria (SRB) under sulfate-reducing conditions is probably one of the most important sources of MMHg in natural aquatic environments, but its influence on natural Hg isotopic composition remains to be ascertained. In this context, the methylating SRB Desulfovibrio dechloracetivorans (strain BerOc1) was incubated under sulfate reducing and fumarate respiration conditions (SR and FR, respectively) to determine Hg species specific (MMHg and IHg) isotopic composition associated with methylation and demethylation kinetics. Our results clearly establish Hg isotope mass-dependent fractionation (MDF) during biotic methylation (-1.20 to +0.58‰ for δ(202)Hg), but insignificant mass-independent fractionation (MIF) (-0.12 to +0.15‰ for Δ(201)Hg). During the 24h of the time-course experiments Hg isotopic composition in the produced MMHg becomes significantly lighter than the residual IHg after 1.5h and shows similar δ(202)Hg values under both FR and SR conditions at the end of the experiments. This suggests a unique pathway responsible for the MDF of Hg isotopes during methylation by this strain regardless the metabolism of the cells. After 9 h of experiment, significant simultaneous demethylation is occurring in the culture and demethylates preferentially the lighter Hg isotopes of MMHg. Therefore, depending on their methylation/demethylation capacities, SRB communities in natural sulfate reducing conditions likely have a significant and specific influence on the Hg isotope composition of MMHg (MDF) in sediments and aquatic organisms.

Higher mass-independent isotope fractionation of methylmercury in the pelagic food web of Lake Baikal (Russia).

Mercury undergoes several transformations that influence its stable isotope composition during a number of environmental and biological processes. Measurements of Hg isotopic mass-dependent (MDF) and mass-independent fractionation (MIF) in food webs may therefore help to identify major sources and processes leading to significant bioaccumulation of methylmercury (MeHg). In this work, δ(13)C, δ(15)N, concentration of Hg species (MeHg, inorganic Hg), and stable isotopic composition of Hg were determined at different trophic levels of the remote and pristine Lake Baikal ecosystem. Muscle of seals and different fish as well as amphipods, zooplankton, and phytoplankton were specifically investigated. MDF during trophic transfer of MeHg leading to enrichment of heavier isotopes in the predators was clearly established by δ(202)Hg measurements in the pelagic prey-predator system (carnivorous sculpins and top-predator seals). Despite the low concentrations of Hg in the ecosystem, the pelagic food web reveals very high MIF Δ(199)Hg (3.15-6.65‰) in comparison to coastal fish (0.26-1.65‰) and most previous studies in aquatic organisms. Trophic transfer does not influence MIF signature since similar Δ(199)Hg was observed in sculpins (4.59 ± 0.55‰) and seal muscles (4.62 ± 0.60‰). The MIF is suggested to be mainly controlled by specific physical and biogeochemical characteristics of the water column. The higher level of MIF in pelagic fish of Lake Baikal is mainly due to the bioaccumulation of residual MeHg that is efficiently turned over and photodemethylated in deep oligotrophic and stationary (i.e., long residence time) freshwater columns.

Tracing sources and bioaccumulation of mercury in fish of Lake Baikal--Angara River using Hg isotopic composition.

This study presents the determination and comparison of isotopic compositions of Hg in sediments, plankton, roach, and perch of two freshwater systems in the Lake Baikal-Angara River aquatic ecosystem: the man-made Bratsk Water Reservoir contaminated by Hg from a chlor-alkali factory and the noncontaminated Lake Baikal. Isotopic ratios of biota exhibit both significant mass-independent fractionation (MIF) (Δ(199)Hg from 0.20 to 1.87‰) and mass-dependent fractionation (MDF) (δ(202)Hg from -0.97 to -0.16‰), whereas sediments exhibit high MDF (δ(202)Hg from -1.99 to -0.83‰) but no MIF. δ(15)N and δ(13)C are correlated with methylmercury in organisms from both sites, indicating bioaccumulation and biomagnification through food webs of both regions. Combining this with isotopic composition of samples shows that δ(202)Hg increases with the trophic level of organisms and also with methylmercury in fish from Lake Baikal. This study demonstrates that MIF in fish samples from Bratsk Water Reservoir allow to trace anthropogenic Hg, since fish with the highest levels of Hg in muscle have the same isotopic composition as the sediment in which anthropogenic Hg was deposited. Less contaminated fish do not exhibit this anthropogenic signature accumulating relatively lower Hg amount from the contaminated sediments. This work reveals that Hg isotopic composition can be used to track the contribution of anthropogenic sources in fish from a contaminated lake.

Approach to measure isotopic ratios in species using multicollector-ICPMS coupled with chromatography.

A new approach was demonstrated for the isotope ratio measurement in different elemental species of Hg using transient signal obtained by chromatography coupled with multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS). The method based on the slope of linear regression by transient intensities of different isotopes shows improved accuracy and reproducibility (0.2-0.5 per thousand as 2 standard deviation (SD)). Internal precision (RSD) of the method is very close to the theoretical value given by the counting statistic and is better by a factor of 6 in comparison with previous conventional methods of calculation. We demonstrated that internal RSD (uncertainty) depends on regression coefficients of the linear function (R(2)). The typical internal precision of isotopic ratio measurements (0.003-0.02%) was achieved for delta(202)Hg when injecting as low as 90 pg of Hg species. With the new methodology, it is possible to (i) measure the isotopic composition when a sample and a bracketing standard have significantly different concentrations, (ii) measure the isotopic composition of different species in samples versus single species in a bracketing standard, and (iii) measure the isotopic ratios for low abundant isotopes. We demonstrated application of this method for different environmental samples and processes.