A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.     

Estrogenic and dioxin-like compounds in sediment from Zierikzee harbour identified with CALUX assay-directed fractionation combined with one and two dimensional gas chromatography analyses

The identity of compounds responsible for estrogenic and dioxin-like activities in sediment from the harbour of the small town Zierikzee in Zeeland, The Netherlands, was investigated using a bioassay directed fractionation approach with the in vitro estrogen and dioxin responsive reporter gene assays ER- and DR-CALUX. For identification of compounds exhibiting activity in the bioassays, either one or two-dimensional GC in combination with quadrupole (MSD), ion trap (ITD) or time-of-flight mass spectrometric detection (ToF-MS) was used, depending on the biological and chemical characteristics and the complexity of the fractions. The natural estrogenic hormone 17-β-estradiol and its metabolite estrone were identified with GC–ITD as the main contributors to the estrogenic activity. After successive rounds of fractionation, the dioxin-like activity could be explained by the presence of various polycyclic aromatic hydrocarbons identified with GC–MSD and two-dimensional comprehensive GC × GC–ToF-MS. Some estrogenic activity of a relatively non-polar nature remained unidentified.     

PM Emissions Emanating from Limited-Access Highways

ABSTRACT

Motor vehicle contributions to primary particulate matter (PM) emissions include exhaust, tire wear, brake and clutch wear, and resuspended road dust. Relatively few field studies have been conducted to quantify fleetaverage exhaust emissions for actual on-road conditions. Therefore, direct measurements of motor vehicle-related PM emissions are warranted. In this study, PM₁₀ and PM_2.5 mass concentrations were measured near two major highways in the St. Louis area over the period from February–April 1997. Samplers were deployed both upwind and downwind of the roadways to capture the transport and dispersion of PM with distance from the roadway. The observed microscale concentration fields were compared to estimates using the PART5 emission factor model together with the CALINE4 highway dispersion model. Traffic- induced PM mass concentrations observed downwind of the roadway were always less than PART5/CALINE4 predictions; average percent differences for observed traffic-induced mass concentrations compared to predicted values were ?34% for PM_2.5 and -70% for PM₁₀. In most cases, the observed PM concentration decay with increasing distance from the roadway was steeper than predicted by dispersion modeling. Motor vehicle-induced emission factors were reconstructed by fitting CALINE4 to the observed concentration data with the emission factor as the sole adjustable parameter. Reconstructed fleet-average motor vehicle emission factors for the urban interstate highway were 0.03–0.04 g/VMT for both PM_2.5 and PM₁₀, while the fleet-average emission factors for the rural interstate highway were 0.2 and 0.3 g/VMT for PM_2.5 and PM₁₀, respectively.