Philipp Böning

Consistent assessment of trace metal contamination in surface sediments and suspended particulate matter: A case study from the Jade Bay in NW Germany

Recently, within the framework of European directives, the importance of marine monitoring programs has increased. In this study, a dense sampling grid was applied for a detailed assessment of the metal contents of surface sediments and suspended particulate matter from the Jade Bay, one of the tidal basins in the southern North Sea. The local lithogenic background was defined and compared with average shale, a common reference material. Based on the calculated non-lithogenic fraction and a cluster analysis, the metals are distributed in two groups: (i) elements of mainly natural origin (Co, Cr, and a major portion of Cd) and (ii) elements associated with anthropogenic activity (As, Cd, Cu, Ni, Pb, Sn, and Zn). However, even the metals of the second group are enriched by at most a factor of two relative to the local background, suggesting minimal anthropogenic impact. Spatial distribution maps show that the harbor area of Wilhelmshaven may be a particularly important source of metal.

Simple approach for the preparation of 15− 15N2-enriched water for nitrogen fixation assessments: evaluation, application and recommendations

Recent findings revealed that the commonly used 15N2 tracer assay for the determination of dinitrogen (N2) fixation can underestimate the activity of aquatic N2-fixing organisms. Therefore, a modification to the method using pre-prepared 15−15N2-enriched water was proposed. Here, we present a rigorous assessment and outline a simple procedure for the preparation of 15−15N2-enriched water. We recommend to fill sterile-filtered water into serum bottles and to add 15−15N2 gas to the water in amounts exceeding the standard N2 solubility, followed by vigorous agitation (vortex mixing ≥ 5 min). Optionally, water can be degassed at low-pressure (≥950 mbar) for 10 min prior to the 15−15N2 gas addition to indirectly enhance the 15−15N2 concentration. This preparation of 15−15N2-enriched water can be done within 1 h using standard laboratory equipment. The final 15N-atom% excess was 5% after replacing 2–5% of the incubation volume with 15−15N2-enriched water. Notably, the addition of 15−15N2-enriched water can alter levels of trace elements in the incubation water due to the contact of 15−15N2-enriched water with glass, plastic and rubber ware. In our tests, levels of trace elements (Fe, P, Mn, Mo, Cu, Zn) increased by up to 0.1 nmol L−1 in the final incubation volume, which may bias rate measurements in regions where N2 fixation is limited by trace elements. For these regions, we tested an alternative way to enrich water with 15−15N2. The 15−15N2 was injected as a bubble directly to the incubation water, followed by gentle shaking. Immediately thereafter, the bubble was replaced with water to stop the 15−15N2 equilibration. This approach achieved a 15N-atom% excess of 6.6 ± 1.7% when adding 2 mL 15−15N2 per liter of incubation water. The herein presented methodological tests offer guidelines for the 15N2 tracer assay and thus, are crucial to circumvent methodological draw-backs for future N2 fixation assessments.

Rapid and accurate determination of Thallium in seawater using SF-ICP-MS

We present a method for the rapid and direct determination of dissolved Thallium (Tl) using high resolution sector field inductively coupled mass spectrometry (SF-ICP-MS) suitable for the measurement of large time series (e.g. during monitoring). Thallium data are presented for a series of natural sea water samples, which were validated with sea water standards CASS-4 and NASS-5. The sea water samples and standards were diluted 10 times prior to measurement with SF-ICP-MS in low resolution mode (R=300, LR). For both CASS-4 and NASS-5 (salinity of 30.5) we calculated a concentration of about 11 ng L(-1) when using Tl values of 14±2 ng L(-1) (at salinity of 35±1) published by Flegal and Patterson for Atlantic and Pacific sea water. For CASS-4 we report a Tl value of 10.6±0.7 ng L(-1) (n=70), for NASS-5 a Tl value of 10.3±0.8 ng L(-1) (n=11). For Tl in both CASS-4 and NASS-5, the overall error in accuracy and precision is less than 4% and 8% (2s), respectively. Further, values of 7.7±0.3 and 6.7±0.2 ng L(-1) Tl were found for the estuarine standard SLEW-3 (salinity of 15) and the river water standard SLRS-4, respectively, for which no certified value exists so far. The detection and quantification limits of our method are 0.1 and 0.3 ng L(-1), respectively. Slight differences in the accuracy of our method and other published methods for the determination of Tl in sea water are discussed. Time-series of natural coastal water samples gave Tl values (6-12 ng L(-1)), which correspond to determined salinities, and hence, appear realistic and oceanographically consistent.

The potential of sedimentary foraminiferal rare earth element patterns to trace water masses in the past

Dissolved rare earth element (REE) concentration data from intermediate and deep seawater form an array characterized by higher middle REE enrichments (MREE/MREE*) in the North Atlantic and a progressive increase in heavy-to-light REE ratios (HREE/LREE) as water masses age. The REEs in foraminifera are fractionated towards higher MREE/MREE* and lower HREE/LREE relative to seawater. Calculations based on a scavenging model show that the REE patterns in uncleaned core-top foraminifera resemble those adsorbed onto calcite, particulate organic material, and hydrous ferric oxides but the full extent of the REE fractionation measured in foraminifera was not reproduced by the model. However, differences in the HREE/LREE, MREE/MREE* ratios and the cerium anomaly between ocean basins are preserved and are in agreement with the seawater REE distribution. Under oxic conditions, the HREE/LREE and MREE/MREE* compositions of uncleaned foraminifera at the sediment/seawater boundary are preserved during burial but the cerium anomaly is sensitive to burial depth. In suboxic sedimentary environments, all uncleaned foraminiferal REE concentrations are elevated relative to core-top values indicating addition of REEs from pore waters. The HREE/LREE ratio is highest when sedimentation rates were greatest [Lippold et al., 2009] and when high Fe/Ca ratios in the uncleaned foraminifera indicate that Fe was mobile. In sediments that have not experienced suboxic conditions during burial, uncleaned foraminifera preserve the seawater signal taken up at the sediment/seawater interface and are therefore suggested to be a suitable archive of changes in the REE signal of past bottom waters. This article is protected by copyright. All rights reserved.

Controls on erosion in the western Tarim Basin: Implications for the uplift of northwest Tibet and the Pamir

We present here bulk sediment major element chemistry, Nd and Sr isotope ratios, and detrital apatite fission-track (AFT) and U-Pb zircon ages to characterize the provenance of the southwestern Taklimakan Desert (northwest China) and the three major rivers draining this region. We establish the spatial and temporal controls on erosion and sediment transport in the modern Tibetan rain shadow. The Hotan River drains the North Kunlun block and is characterized by zircon populations at 160–230 Ma and 370–520 Ma. The Yarkand River shares these grains with the Hotan, but also has a very prominent zircon population at 40–160 Ma, which is common in Karakoram basement, indicating heavy sediment flux from these ranges to that drainage. This implies a strong control on erosion by topographic steepness and precipitation mediated through glaciation. Our zircon data confirm earlier studies that indicated that the Taklimakan sand is derived from both the Kunlun and Pamir Mountains. AFT ages are younger in the Hotan River than in the Kashgar River, which drains the Pamir, and in both are younger than in the Transhimalaya and parts of the western edge of the Tibetan Plateau. Exhumation is estimated at ~1000 m/m.y in the North Kunlun and ~500 m/m.y. in the eastern Pamir, which have been exhuming more slowly than the western ranges in the recent past. Holocene aggradation terracing was dated using quartz optically stimulated luminescence methods and is mostly associated with times of fluctuating climate after 4 ka, with phases of valley filling dated at 2.6, 1.4, and 0.4 ka. The heights and volumes of the terraces show that sediment storage in the mountains is not a significant buffer to sediment transport, in contrast to the more monsoonal Indus system directly to the south. South of the Mazatag Ridge a significant eolian deposit accumulated ~500 yr ago, but this has been deflated in more recent times. Comparison of the modern river data with those previously measured from Cenozoic foreland sedimentary rocks shows that no sediment similar to that of the modern Yarkand River is seen in the geologic record, which is inferred to be younger than 11 Ma, and probably much less. Uplift of the North Kunlun had started by ca. 17 Ma, somewhat after that of the Pamir and Songpan Garze of northwestern Tibet, dated to before 24 Ma. Sediment from the Kunlun reached the foreland basin between 14 and 11 Ma. North Kunlun exhumation accelerated before 3.7 Ma, likely linked to faster rock uplift.

Testing chemical weathering proxies in Miocene–Recent fluvial-derived sediments in the South China Sea

Abstract Reconstructing variations in the intensity of chemical weathering in river basins is crucial if we are to understand how climate change impacts environment and whether there are feedbacks between climate and weathering processes. Quantifying chemical weathering is, however, a complicated process, involving a number of competing proxies. We compare weathering records from the Pearl River delta of southern China and Ocean Drilling Program (ODP) Sites 1144 and 1146 on the northeastern slope of the South China Sea in order to test which proxies are the most widely applicable and robust. Comparison with speleothem rainfall records indicates that K/Al tracks precipitation variations most closely and out-performs the widely used Chemical Index of Alteration (CIA). Correlation of K/Al and kaolinite/illite indicates that this clay ratio is also an effective proxy of weathering intensity across all sites and timescales. Kaolinite/smectite, and to a lesser extent smectite/(illite+chlorite), are also indicative of weathering intensity, but show more scatter between sites that may be linked to provenance effects. Mg/Al is relatively immune to grain-size effects, but does not correlate well with other proxies. K/Rb is a reasonably reliable indicator of chemical weathering intensity and may be more sensitive than CIA or K/Al to weathering changes over short timescales and when weathering is not too intense. 87Sr/86Sr can be useful but can be influenced by both grain size and provenance effects. In general marine archives of fluvial sediment may record variations in weathering linked to climate, but these are increasingly signals of reworking going further offshore.

Climatic and glacial impact on erosion patterns and sediment provenance in the Himalayan rain shadow, Zanskar River, NW India

Erosion is a key step in the destruction and recycling of the continental crust, yet its primary drivers continue to be debated. The relative balance between climatic and solid Earth forces in determining erosion patterns and rates, and in turn orogenic architecture, is unresolved. The monsoon-dominated frontal Himalaya is a classic example of how surface processes may drive focused denudation and potentially control structural evolution. We investigate whether there is a clear relationship between climate and erosion in the drier Himalayan rain shadow on the periphery of the Tibetan Plateau, where a coupled climate-erosion relationship is less clear. We present a new integrated data set combining bulk petrography, geomorphometric analysis, detrital U-Pb zircon geochronology, and bulk Nd and Sr isotope geochemistry from modern river sediments that provides constraints on spatial patterns of sediment production and transport in the Zanskar River. Zanskar River sands are dominated by Greater Himalayan detritus sourced from the glaciated Stod River catchment, which represents only 13% of the total basin area. Prevalent zircon peaks from Cambrian-Ordovician (440-500 Ma) and Mississippian- Permian (245-380 Ma) units indicate more abundant pre-Himalayan granitoids in the northwest Indian Himalaya than in the central and eastern Himalaya. Erosion from the widely exposed Tethyan Himalaya, however, appears modest. Spatial patterns of erosion do not correlate with highest channel steep-ness. Our data demonstrate that Zanskar differs from the monsoon-soaked frontal Himalaya and the arid, extremely slow-eroding Tibetan orogenic interior in that focused erosion and sediment production are driven by glaciers. Subsequent remobilization of glacially derived sediments is likely controlled by monsoonal rainfall, and we suggest sediment reworking plays an important role. These data support a strong climatic control on modern orogenic erosion in the Himalayan rain shadow on the periphery of the Tibetan Plateau.

Tracking hospital effluent-derived gadolinium in Atlantic coastal waters off Brazil

The use of gadolinium (Gd) complexes as contrast agents in magnetic resonance imaging (MRI) has resulted in point source releases of anthropogenic Gd into the environment and presents the opportunity to trace the fate of wastewater plumes. Here we collected seawater samples along the coast of Northeast Brazil to investigate the influence of two submarine sewage outfalls on the distribution of Gd and other rare earth elements (REE) in the coastal waters. The shale-normalized REEs only show a small light over heavy REE enrichment and negative Ce anomalies, likely reflecting the influence of freshwater inputs. Positive Gd anomalies are observed at most of the sampling sites, indicating the ubiquitous presence of anthropogenic Gd in coastal waters. The highest Gd anomalies are found in the vicinity of the submarine sewage outfalls and decrease with increasing distance from point source. The total daily discharge of 216 ± 82 g Gd and 92.0 ± 19.3 g Gd was calculated for the Rio Vermelho (ERV) and Boca do Rio (EBR) submarine outfalls, respectively, which on population bases equates to 11.5 ± 4.3 g Gd d-1 for ERV and 15.5 ± 3.3 g Gd d-1 for EBR per 100 000 persons. It is estimated that in 2016 the annual emission of anthropogenic Gd by hospitals and clinics in Brazil varied between 527 kg and 5.3 tons. It was roughly estimated that between 698 and 2021 g Gd d-1 are discharged into the Tropical and South Atlantic waters due to submarine outfall sewage along the coast of Brazil.