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To link to full-text access for this article, visit this link: http://dx.doi.org/10.1016/S0967-0637(99)00072-2 Byline: F. Dehairs, N. Fagel, A.N. Antia, R. Peinert, M. Elskens, L. Goeyens Keywords: Ba-proxy; Carbon export; Margin system Abstract: We present barium data for sediment traps deployed in a northeast Atlantic margin environment (Bay of Biscay). Fluxes of excess barium were measured with the objective of calculating carbon export production rates from the surface mixed layer and thus contribute to the understanding of organic carbon transport in a margin environment. Therefore, it was necessary to properly understand the different processes that affected the barium fluxes in this margin environment. Seasonal variability of POC/Ba flux ratios and decrease of barium solubilisation in the trap cups with increasing depth in the water column probably indicate that the efficiency of barite formation in the organic micro-environment varies with season and that the process is relatively slow and not yet completed in the upper 600m of water column. Thus barite presence in biogenic aggregates will significantly depend on water column transit time of these aggregates. Furthermore, it was observed that significant lateral input of excess-Ba can occur, probably associated with residual currents leaving the margin. This advected excess-Ba affected especially the recorded fluxes in the deeper traps (>1000m) of the outer slope region. We have attempted to correct for this advected excess-Ba component, using Th (reported by others for the same samples) as an indicator of enhanced lateral flux and assigning a characteristic Ba/Th ratio to advected material. Using transfer functions relating excess-Ba flux with export production characteristic of margin areas, observed Ba fluxes indicate an export production between 7 and 18gC m.sup.-2 yr.sup.-1. Such values are 3-7 times lower than estimates based on N-nutrient uptake and nutrient mass balances, but larger and more realistic than is obtained when a transfer function characteristic of open ocean systems is applied. The discrepancy between export production estimates based on excess-Ba fluxes and nutrient uptake could be resolved if part of the carbon is exported as dissolved organic matter. Results suggest that margin systems function differently from open ocean systems, and therefore Ba-proxy rationales developed for open ocean sites might not be applicable in margin areas. Article History: Received 6 November 1998; Revised 17 May 1999; Accepted 17 May 1999

New production (NP) for NW Iberian shelf waters from 42-degree to 43-degree North (3500 km2), at the fortnight, upwelling-season (March-October) and inter-annual time-scales, is calculated. Average NP over the upwelling-season ranged from 330 to 815 mg C m-2d-2 in the 1982-1999 period.

Abstract: This paper presents results on tracer experiments using 13C and 15N to estimate uptake rates of dissolved inorganic carbon (DIC) and nitrogen (DIN). Experiments were carried out at station K2 (47°N, 161°E) in the NW Pacific subarctic gyre during July–August 2005. Our goal was to investigate relationships between new and export production. New production was inferred from the tracer experiments using the f ratio concept (0–50m); while export production was assessed with neutrally buoyant sediment traps (NBSTs) and the e ratio concept (at 150m). During trap deployments, K2 was characterized both by changes in primary production (523–404mgCm−2 d−1), new production (119–67mgCm−2 d−1), export production (68–24mgCm−2 d−1) and phytoplankton composition (high to low proportion of diatoms). The data indicate that 17–23% of primary production is exportable to deeper layers (f ratio) but only 6–13% collected as a sinking particle flux at 150m (e ratio). Accordingly, >80% of the carbon fixed by phytoplankton would be mineralized in the upper 50m (1–f), while <11% would be within 50–150m (f–e). DIN uptake flux amounted to 0.5mMm−2 h−1, which was equivalent to about 95% particulate nitrogen (PN) remineralized and/or grazed within the upper 150m. Most of the shallow PN remineralization occurred just above the depth of the deep chlorophyll maximum (DCM), where a net ammonium production was measured. Below the DCM, while nitrate uptake rates became negligible because of light limitation, ammonium uptake did continue to be significant. The uptake of ammonium by heterotrophic bacteria was estimated to be 14–17% of the DIN assimilation. Less clear are the consequences of this uptake on the phytoplankton community and biogeochemical processes, e.g. new production. It was suggested that competition for ammonium could select for small cells and may force large diatoms to use nitrate. This implies that under Fe stress as observed here, ammonium uptake is preferred and new production progressively suppressed despite the surplus of nitrate. [Copyright &y& Elsevier]

Abstract: Since the CALUX (Chemically Activated LUciferase gene eXpression) bioassay is a fast, sensitive and inexpensive tool for the analysis of a high number of samples, validation of new methods is urgently needed. In this study, a new method for the analysis of PCDD/Fs and dioxin-like PCBs in atmospheric deposition samples with the CALUX bioassay was developed, optimized and validated. The method consists of 4 steps: filtration, extraction, clean up and bioassay analysis. To avoid the use of large amounts of toxic solvents, new techniques were used for filtration and extraction: a C18 filter was used instead of a liquid/liquid extraction and an Accelerated Solvent Extractor (ASE) was used instead of the traditional soxhlet extraction. After pre-oxidation of the sample extract, clean up was done using a multi-layer silica gel column coupled to a carbon column. The PCDD/F and PCB fractions were finally analyzed with the H1L7.5c1 and/or the H1L6.1c3 mouse hepatoma cell lines. The limit of quantification was 1.4pg CALUX-BEQm−2 d−1 for the PCBs and 5.6pgCALUX-BEQm−2 d−1 for the PCDD/Fs, when using the new sensitive H1L7.5c1 cell line. The GC–HRMS recovery for all PCDD/F congeners was between 55% and 112%, with a mean recovery of 90%. CALUX recoveries of spiked procedural blanks were between the accepted ranges of 80–120%. Repeatability and reproducibility were satisfactory and no interferences from metals were detected. The first results from the Flemish measurement program showed good correlation between CALUX and GC–HRMS. [ABSTRACT FROM AUTHOR]

Abstract: High resolution profiles of Mn, Tl and Fe concentrations have been assessed in the pore waters of river Leie sediments at Warneton and Menen (at the border of Belgium and France) by DET (Diffusive Equilibrium in Thin Films) and DGT (Diffusive Gradients in Thin Films) techniques. The oxidized, solid Mn (IV), Tl (III) and Fe (III) compounds were reduced in the suboxic (+255 to −20 mV versus Standard Hydrogen Electrode (SHE)) riverine sediments and since these reduced species are much more soluble also they are released into the pore waters. The highest DET (total dissolved) concentrations of Fe (76 mg l−1), Mn (2 mg l−1) were observed at the station of Menen, while Tl maxima differed only slightly between the 3 surveys (21 to 27 μg l−1). The average ratios of Fe/Mn/Tl in the pore waters at the 3 sampling stations are fairly constant for both the DET and DGT samplings. However, the results indicate that compared to Fe and Tl a greater proportion of the Mn measured by DET is accumulated by DGT, reflecting the ready supply of Mn from solid phase to solution. [Copyright &y& Elsevier]

Abstract Paperboard used as packaging, a non-inert material, can transfer chemicals into food. Over the years, endocrine disrupting compounds (EDCs), such as NonylPhenols (NPs), BisPhenol A (BPA) and phthalates have been shown to migrate from packaging materials into food. Due to chronic exposure and mixture effects of these EDCs, they could cause health effects even at very low doses. Many EDCs are still unknown and many more are still unregulated. The ERE-CALUX bioassay was used as a bioanalytical tool to investigate estrogenic activities of paperboard food packaging and its characteristics, including recycling rate and printing ink. A "worst case" scenario with full extraction is compared to a dry food migration experiment. By measuring an overall estrogenic activity, known and unknown estrogenic chemicals and mixture effects are taken into account and the data are compared to molecule specific analysis. Estrogenic activities ranged from 682 ± 66 pg E2 eq./dm2 to 3250 ± 400 pg E2 eq./dm2 for "worst case" extraction and from 347 ± 30 pg E2 eq./dm2 to 1350 ± 70 pg E2 eq./dm2 for migration experiments. A two-factor ANOVA revealed a relationship between estrogenic activity and the recycling rate of the paperboard, but no significant difference with printing ink was observed for these paperboard samples. Bis(2-ethylhexyl)phthalate (DEHP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP) and 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH) were determined in all extraction and migrations experiment samples. A Spearman rank correlation analysis showed a relationship between the estrogenic activity and the total phthalates as well as with each compound individually. Highlights • Estrogenic activities of paperboard in "worst case" extractions and in migrations. • Activities have relative standard deviations below 18% with a median value of 9.7%. • Recycling rate of paperboard food packaging highly related to estrogenic activity. • Estrogenic activities are compared to molecule specific analysis of plasticizers. • A relationship was shown between the estrogenic activity and the phthalates. [ABSTRACT FROM AUTHOR]

The Zenne River, crossing the Brussels region (Belgium) is an extremely urbanized river impacted by both domestic and industrial effluents. The objective of this study was to monitor the occurrence and activity of Endocrine Active Substances (EAS) in river water and sediments in the framework of the Environmental Quality Standards Directive (2008/105/EC and 2013/39/EU). Activities were determined using Estrogen and Dioxin Responsive Elements (ERE and DRE) Chemical Activated Luciferase Gene Expression (CALUX) bioassays. A potential contamination source of estrogen active compounds was identified in the river at an industrial area downstream from Brussels with a peak value of 938 pg E2 eq./L water (above the EQS of 0.4 ng/L) and 195 pg E2 eq./g sediment. Estrogens are more abundantly present in the sediments than in the dissolved phase. Principal Component Analysis (PCA) showed high correlations between Suspended Particulate Matter (SPM), Particulate (POC) and Dissolved Organic Carbon (DOC) and estrogenic EAS. The dioxin fractions comply with previous data and all were above the United States Environmental Protection Agency (US EPA) low-level risk, with one (42 pg TCDD eq./g sediment) exceeding the high-level risk value for mammals. The self-purifying ability of the Zenne River regarding estrogens was examined with an in vitro biodegradation experiment using the bacterial community naturally present in the river. Hill coefficient and EC 50 values (Effective Concentration at 50%) revealed a process of biodegradation in particulate and dissolved phase. The estrogenic activity was decreased by 80%, demonstrating the ability of self-purification of estrogenic compounds in the Zenne River. [ABSTRACT FROM AUTHOR]

Estrogen-like endocrine disrupting chemicals (EEDCs) can be found abundantly in the environment. Due to their low-dose effects and the large amount of unknown EEDCs, it is difficult to assess and manage possible human health risks. For young children, who are particularly vulnerable to endocrine disruption due to their development rate, indoor dust is one of the main routes of exposure. In this study, an estrogen responsive elements chemically activated luciferase gene expression (ERE-CALUX) bioassay was characterized and implemented for the analysis of 12 dust samples from kindergartens in Flanders and Brussels (Belgium). The human ovarian carcinoma BG 1CALUX cell line showed reproducible results and a low limit of detection (LOD). The effective concentration at 50% of the maximum response (EC 50 ) yielded 497 fg/well, while the LOD was 16 fg/well. For all dust samples, full dose–response curves and their corresponding EC 50 values could be calculated. All samples yielded bio-analytical equivalent concentrations (BEQs) that were significantly higher than the procedural blank level and ranged from 426 to 8710 pg E2 equivalents/g dust. A clear relationship was observed between a semi-quantitative interior score and the ERE-CALUX response of the samples. In addition, the concentration of phthalates, a major group of EEDCs used as plasticizers in plastics, was determined in the samples by GC–MS. Diisoheptyl phthalate (DiHP) and di(2-ethylhexyl) phthalate (DEHP) were present in every dust sample. A good correlation was found between ERE-CALUX activities and phthalate concentrations, when all phthalates except diisononyl phthalate (DiNP) and diisodecyl phthalate (DiDP), which do not bind to the estrogen receptor, were taken into account. This shows that the ERE-CALUX can provide relevant results concerning exposure to EEDCs from indoor dust. This article is part of a Special Issue entitled ‘Endocrine disruptors & steroids’. [ABSTRACT FROM AUTHOR]

Abstract: Since the CALUX (Chemically Activated LUciferase gene eXpression) bioassay is a fast, sensitive and inexpensive tool for the analysis of a high number of samples, the use of this technique in routine analysis of atmospheric deposition samples may be a valuable alternative for GC–HRMS. In this study, a validated CALUX method was used for the analysis of PCDD/Fs and dioxin-like PCBs in more than 90 atmospheric deposition samples for different locations in Flanders. The samples were taken in residential and agricultural areas, where a threshold limit of 21pgWHO-TEQm−2 d−1 for the sum of PCDD/Fs and dioxin-like PCBs was set, and in industrial zones and natural reserves, where no official threshold limit is available. The results from the Flemish measurement program showed correlation between CALUX and GC–HRMS for all the samples, originating from the different areas (R 2 of 0.81, 0.53 and 0.64 for dl-PCBs, PCDD/Fs and sum of both fractions, respectively). Median CALUX/GC–HRMS ratios of 2.0, 0.9 and 1.3 were reported for the PCDD/Fs, dioxin-like PCBs and the sum of both fractions, respectively. The results show that the CALUX bioassay is a valuable alternative tool for the classic GC–HRMS analysis of atmospheric deposition samples in the Flemish measurement network. [Copyright &y& Elsevier]

Abstract: This study focuses on the fate of exported organic carbon in the twilight zone at two contrasting environments in the North Pacific: the oligotrophic ALOHA site (22°45′N, 158°W; Hawaii; studied during June–July 2004) and the mesotrophic Subarctic Pacific K2 site (47°N, 161°W; studied during July–August 2005). Earlier work has shown that non-lithogenic, excess particulate Ba (Baxs) in the mesopelagic water column is a potential proxy of organic carbon remineralization. In general, Baxs contents were significantly larger at K2 than at ALOHA. At ALOHA, the Baxs profiles from repeated sampling (five casts) showed remarkable consistency over a period of three weeks, suggesting that the system was close to being at steady state. In contrast, more variability was observed at K2 (six casts sampled), reflecting the more dynamic physical and biological conditions prevailing in this environment. While for both sites Baxs concentrations increased with depth, at K2 a clear maximum was present between the base of the mixed layer at around 50 and 500m, reflecting production and release of Baxs. Larger mesopelagic Baxs contents and larger bacterial production in the twilight zone at the K2 site indicate that more material was exported from the upper mixed layer for bacterial degradation deeper, compared to the ALOHA site. Furthermore, application of a published transfer function [Dehairs, F., Shopova, D., Ober, S., Veth, C., Goeyens, L., 1997. Particulate barium stocks and oxygen consumption in the Southern Ocean mesopelagic water column during spring and early summer: relationship with export production. Deep-Sea Research II 44(1–2), 497–516] relating oxygen consumption to the observed Baxs data indicated that the latter were in good agreement with bacterial respiration, calculated from bacterial production. These results corroborate earlier findings highlighting the potential of Baxs as a proxy for organic carbon remineralization. The range of POC remineralization rates calculated from twilight zone excess particulate Ba contents also compared well with the depth dependent POC flux decrease as recorded by neutrally buoyant sediment traps, except in one case (out of four). This discrepancy could indicate that differences in sinking velocities cause an uncoupling of the processes occurring in the fine suspended particle pool from those affecting the larger particle pool which sustains the vertical flux, thus rendering comparison between both approaches risky. [Copyright &y& Elsevier]

Abstract: The VERtical Transport In the Global Ocean (VERTIGO) study examined particle sources and fluxes through the ocean''s “twilight zone” (defined here as depths below the euphotic zone to 1000m). Interdisciplinary process studies were conducted at contrasting sites off Hawaii (ALOHA) and in the NW Pacific (K2) during 3-week occupations in 2004 and 2005, respectively. We examine in this overview paper the contrasting physical, chemical and biological settings and how these conditions impact the source characteristics of the sinking material and the transport efficiency through the twilight zone. A major finding in VERTIGO is the considerably lower transfer efficiency (T eff) of particulate organic carbon (POC), POC flux 500/150m, at ALOHA (20%) vs. K2 (50%). This efficiency is higher in the diatom-dominated setting at K2 where silica-rich particles dominate the flux at the end of a diatom bloom, and where zooplankton and their pellets are larger. At K2, the drawdown of macronutrients is used to assess export and suggests that shallow remineralization above our 150-m trap is significant, especially for N relative to Si. We explore here also surface export ratios (POC flux/primary production) and possible reasons why this ratio is higher at K2, especially during the first trap deployment. When we compare the 500-m fluxes to deep moored traps, both sites lose about half of the sinking POC by >4000m, but this comparison is limited in that fluxes at depth may have both a local and distant component. Certainly, the greatest difference in particle flux attenuation is in the mesopelagic, and we highlight other VERTIGO papers that provide a more detailed examination of the particle sources, flux and processes that attenuate the flux of sinking particles. Ultimately, we contend that at least three types of processes need to be considered: heterotrophic degradation of sinking particles, zooplankton migration and surface feeding, and lateral sources of suspended and sinking materials. We have evidence that all of these processes impacted the net attenuation of particle flux vs. depth measured in VERTIGO and would therefore need to be considered and quantified in order to understand the magnitude and efficiency of the ocean''s biological pump. [Copyright &y& Elsevier]

Examines the measurements of nutrients and dissolved organic matter at and across the European shelf break in relation to hydrography and biochemical activity. Description of the sampling area, cruises and data products of the ocean margin exchange project; Inorganic nutrient distributions in the region of the Celtic Sea shelf break; Changes in nutrient distributions resulting from biological production.

Polycyclic aromatic hydrocarbons (PAH) are a complex group of organic compounds, consisting of at least three fused aromatic rings, which are formed during combustion of organic matter. While some PAHs have been reported to have carcinogenic and/or mutagenic properties, another possible negative health impact is their endocrine disrupting potential. Therefore, the aim of this study was to determine both the agonistic and antagonistic endocrine activity of 9 environmentally relevant PAHs using three different CALUX bioassays: The AhR-CALUX, The ERα-CALUX and PPARγ-CALUX. For the PPARγ-CALUX anthracene, fluoranthene, pyrene and fluorene showed weak agonistic activity, whilst benzo(a)pyrene (B(a)P) was the only one exhibiting weak antagonistic activity. For the AhR-CALUX, chrysene was the only PAH that showed relatively strong agonist activity (except for B(a)P which was used as a standard). Pyrene, anthracene and fluoranthene showed weak AhR agonist activity. In the ERα-CALUX bioassay, fluoranthene had agonistic activity whilst B(a)P exhibited both agonistic and antagonistic activity (lowering E2 activity by 30%). Phenanthrene and anthracene had weak ERα agonist activities. These results indicate that certain PAHs have multiple modes of action and can activate/inhibit multiple receptor signaling pathways known to play critical roles in mediating endocrine disruption. Image 1 • PAHs have multiple modes of action and can activate/inhibit multiple receptor signaling pathways. • Anthracene, fluoranthene, pyrene and fluorene showed weak agonistic activity in PPARy-CALUX. • Chrysene and B(a)P showed clear agonistic activity in AhR-CALUX; pyrene, anthracene and fluoranthene showed weak AhR-activity. • Fluoranthene, benzo(a)pyrene, phenanthrene and anthracene were found to be (weakly) estrogenic. • B(a)P is a partial ER agonist that can both induce and inhibit ER functional activity. [ABSTRACT FROM AUTHOR]