Seasonal and ontogenetic changes of mycosporine-like amino acids in planktonic organisms from an alpine lake

We studied the quantitative and qualitative mycosporine-like amino acid (MAA) composition in phytoplankton and the copepod Cyclops abyssorum tatricus from an alpine lake over a 15-month period. Up to eight MAAs were identified in the samples, with shinorine being predominant. The MAAs occurred year round and showed a strong seasonal pattern. Compared with ice-cover periods, concentrations during the summer were on average 3.6 and 3.0 times higher in phytoplankton and C. abyssorum tatricus, respectively. During the summer, the contents of MAAs in phytoplankton decreased with depth, suggesting their photoprotective role. Chlorophyll a-specific concentrations of MAAs in phytoplankton correlated significantly with the incident solar radiation and ultraviolet (UV) water transparency (r(2) ≤ 0.36), however, the strongest relationship was found with water temperature (r(2) = 0.67). In zooplankton, highest contents of MAAs were found in eggs, nauplii, and young copepodids, presumably providing a high level of photoprotection for progeny. Proportions of the dominant MAAs in the copepod showed seasonal and ontogenetic variations, which were consistent with relative changes in the predominant MAA, but not other abundant MAAs, in phytoplankton. Considering a time lag of approximately 1 month between the synthesis and subsequent accumulation of these compounds, MAA concentrations in late copepodid to adult life stages were significantly correlated to those in phytoplankton. Annual patterns in MAAs with high concentrations during periods of elevated environmental stress are consistent with the idea that these compounds play an important role in protecting aquatic organisms against UV damage.     

Weathering of Oil in a Surficial Aquifer

The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C_6‐30 n‐alkanes, toluene, and o‐xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n‐C_10–24 cyclohexanes, tri‐ and tetra‐ methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ ¹³C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a “starting oil concentration” that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.     

A revisitation of TRIX for trophic status assessment in the light of the European Water Framework Directive: application to Italian coastal waters

The trophic status classification of coastal waters at the European scale requires the availability of harmonised indicators and procedures. The composite trophic status index (TRIX) provides useful metrics for the assessment of the trophic status of coastal waters. It was originally developed for Italian coastal waters and then applied in many European seas (Adriatic, Tyrrhenian, Baltic, Black and Northern seas). The TRIX index does not fulfil the classification procedure suggested by the WFD for two reasons: (a) it is based on an absolute trophic scale without any normalization to type-specific reference conditions; (b) it makes an ex ante aggregation of biological (Chl-a) and physico-chemical (oxygen, nutrients) quality elements, instead of an ex post integration of separate evaluations of biological and subsequent chemical quality elements. A revisitation of the TRIX index in the light of the European Water Framework Directive (WFD, 2000/60/EC) and new TRIX derived tools are presented in this paper. A number of Italian coastal sites were grouped into different types based on a thorough analysis of their hydro-morphological conditions, and type-specific reference sites were selected. Unscaled TRIX values (UNTRIX) for reference and impacted sites have been calculated and two alternative UNTRIX-based classification procedures are discussed. The proposed procedures, to be validated on a broader scale, provide users with simple tools that give an integrated view of nutrient enrichment and its effects on algal biomass (Chl-a) and on oxygen levels. This trophic evaluation along with phytoplankton indicator species and algal blooms contribute to the comprehensive assessment of phytoplankton, one of the biological quality elements in coastal waters.     

Time constraints for Mesoproterozoic upper amphibolite facies metamorphism in NW Namibia: a multi-isotopic approach

This study presents the chronological evolution of the upper amphibolite facies Orue Unit in NW Namibia. Metasedimentary and meta-igneous rocks of the Orue Unit were investigated using the Pb–Pb stepwise leaching technique on garnet and rutile, U–Pb multi-grain analysis on rutile, Sm–Nd–Lu–Hf leaching technique on garnet, SHRIMP analysis on zircon and Ar–Ar dating on amphibole. Each of these techniques pertains to different processes that occurred before, during, or after the metamorphic peak. Our age data can be integrated with petrological constraints to provide a more complete understanding of the metamorphic cycle. Our pre-peak metamorphic zircon ages, peak metamorphic garnet ages and peak to late peak metamorphic amphibole ³⁹Ar–⁴⁰Ar ages bracket the upper amphibolite facies metamorphic event including hydration or dehydration processes into a time span of only ca. 20 Ma. The age data obtained by peak metamorphic mineral analyses cluster around 1340–1320 Ma. Based on age data and field observation, we interpret the upper amphibolite facies metamorphism as a large-scale regional mid-crustal event. Spot analyses of inherited zircon cores obtained by SHRIMP reflect the sedimentary origin of the respective rocks of the Orue Unit and derivation from Palaeoproterozoic protoliths. The metamorphic rocks south of the anorthositic Kunene Intrusive Complex (KIC) have previously been ascribed to the Palaeoproterozoic Epupa Complex at the SW margin of the Congo craton and were thus thought to be older than the Mesoproterozoic KIC. Our data show that the high-grade metamorphic overprint took place 30–50 Ma after emplacement of the KIC. Rutile growth ages of 1248 Ma in one sample reflect fluid activity which seems to be a local phenomenon since there is no other evidence of geological activity throughout the Orue Unit at that time. The rutile ages predate the emplacement of satellite intrusions in that area by 30 Ma and there is no causal relation between these two events.     

Preliminary health risk assessment for polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins/furans in seafood from Guangzhou and Zhoushan, China

Dietary intake is one of the important routes of human exposure to brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs). The use of PBDEs may also result in exposure to polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs), as these compounds are impurities in technical mixtures of BFRs and can also be formed unintentionally by the same processes that generate chlorinated dioxins. This study determined the concentrations of polybrominated compounds in common seafood in Guangzhou and Zhoushan, and assessed the health risks of these chemicals via consumption of contaminated seafood. Seafood samples (fish, bivalves, shrimp, crab, and cephalopods) purchased from local markets in 2003 and 2004 were analyzed for PBDEs and PBDDs/DFs. The highest concentration of total PBDEs (46.3 ng g(-1) lipid wt.) was detected in fish from Guangzhou, in which BDEs 47 and 209 were the two predominant congeners. The total daily intakes of PBDEs, PBDDs, and PBDFs were, 946, 6.39, and 6.54 pg kg(-1) body weight (bw) in Guangzhou, and 489, 4.99, and 7.65 pg kg(-1) bw in Zhoushan, respectively. The hazard ratios for PBDDs and PBDFs were both greater than unity, indicating that these compounds may pose some health risks to the local population.     

Carbon Isotope Analysis to Evaluate Nanoscale Fe(O) Treatment at a Chlorohydrocarbon Contaminated Site

Remediation of groundwater contaminated by chlorinated hydrocarbons via in situ technologies such as direct injection of nanoscale zero valent iron (ZVI, Fe(O)) particles is increasingly common. However, assessing target compound degradation by abiotic processes is difficult because (1) the injection may displace the contaminant plume so that concentration measurements alone are often inconclusive and (2) biodegradation may also occur, making it challenging to identify and evaluate the abiotic degradation component. In this study, trichloroethylene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA) were treated in a highly heterogeneous hydrogeologic setting. The purpose of this study was to evaluate the potential for compound-specific stable isotope analysis (CSIA) to monitor the effectiveness of ZVI injection by assessing TCE and 1,1,1-TCA degradation. Prior to ZVI injection, carbon isotope measurements demonstrated biodegradation of TCE by native microorganisms. This in situ biodegradation was quantified by measuring the enrichment of ¹³C in TCE samples downstream of the suspected source. When ZVI was injected through only two injection wells, no changes in TCE and 1,1,1-TCA isotope signatures were detected compared to preinjection values. In contrast, when ZVI was injected through 11 wells covering a greater portion of the contaminated area, 5 out of 10 monitoring wells showed further enrichment of ¹³C in either TCE or 1,1,1-TCA, indicating additional target compound transformation. The abiotic nature of this TCE transformation was confirmed through temporal trends in carbon isotope values of the putative transformation products cis-dichloroethylene (cis-DCE), ethene and ethane. This demonstrates the usefulness of CSIA in distinguishing abiotic vs. biotic transformation in the field.     

Double-layer structure in the boundary layer over the baltic sea

Double-layered structures found over the Baltic Sea are investigated using radiosoundings and lidar measurements. Situations with double-layer structures are also simulated with the regional model REMO in a realistic manner. The double layer consists of two adjacent well-mixed layers, with a sharp inversion in between.Results from radiosoundings show that the double-layer structure over the Baltic Sea mainly occurs during the autumn with thermally unstable stratification near the surface. The structure is present in about 50 % of the radiosoundings performed during autumn. The presence of the double-layer structure cannot be related to any specific wind direction, wind speed or sea surface temperature.The lidar measurements give a more continuous picture of the time evolution of the double-layer structure, and show that the top of the lower layer is not a rigid lid for vertical transport. Two possible explanations of the double-layer structure are given, (i) the structure is caused by `advection' of land boundary-layer air over the convective marine boundary layer or, (ii) by development of Sc clouds in weak frontal zones connected to low pressure systems. Also the forming of Cu clouds is found to be important for the development of a double-layer structure.     

Spatial transferability of the physically based model TRIGRS using parameter ensembles

The development of better, more reliable and more efficient susceptibility assessments for shallow landslides is becoming increasingly important. Physically based models are well-suited for this, due to their high predictive capability. However, their demands for large, high-resolution and detailed input datasets make them very time-consuming and costly methods. This study investigates if a spatially transferable model calibration can be created with the use of parameter ensembles and with this alleviate the time-consuming calibration process of these methods. To investigate this, the study compares the calibration of the model TRIGRS in two different study areas. The first study area was taken from a previous study where the dynamic physically based model TRIGRS was calibrated for the Laternser valley in Vorarlberg, Austria. The calibrated parameter ensemble and its performance from this previous study are compared with a calibrated parameter ensemble of the model TRIGRS for the Passeier valley in South Tyrol, Italy. The comparison showed very similar model performance and large similarities in the calibrated geotechnical parameter values of the best model runs in both study areas. There is a subset of calibrated geotechnical parameter values that can be used successfully in both study areas and potentially other study areas with similar lithological characteristics. For the hydraulic parameters, the study did not find a transferable parameter subset. These parameters seem to be more sensitive to different soil types. Additionally, the results of the study also showed the importance of the inclusion of detailed information on the timing of landslide initiation in the calibration of the model.