Converting Toxic Equivalents (TEQ) of dioxins and dioxin-like compounds in fish from one Toxic Equivalency Factor (TEF) scheme to another

Toxic Equivalency Factors (TEFs) are an essential part of the Toxic Equivalent (TEQ) concept and have evolved for dioxins/dioxin-like compounds over the last two and half decades. Therefore, it is difficult to compare past and current TEQs that are reported using different TEFs without explicitly mentioning underlying congener concentrations. Using what likely is the largest known dioxin/furan (PCDD/F) and dioxin-like polychlorinated biphenyl (dl-PCB or DLP) fish database, here we present regression models that can facilitate conversion of a fish TEQ from an old to a newer TEF scheme. The results show that the mammalian PCDD/F-TEQ based on the latest TEF(WHO-05) is about 7.5% lower than that based on TEF(WHO-98). The mammalian DLP-TEQ(WHO-05) is on average 25-26% lower than almost identical DLP-TEQ(WHO-94) and DLP-TEQ(WHO-98). Total-TEQ(WHO-05) is on average 22% lower than Total-TEQ(WHO-98). According to the current toxicological standards for dioxins/furans, all previous major TEF schemes except TEF(Germany-85) and TEF(USEPA-87) were conservative (i.e., higher) in estimating TEQs. The major (> 75%) contribution to PCDD/F-TEQ(WHO-05) is from 2,3,7,8-TCDD (33%), 1,2,3,7,8-PCDD (26%), 2,3,7,8-TCDF (10%), and 2,3,4,7,8-PCDF (9%). The DLP-TEQ(WHO-05) is dominated by PCB-126 which on average contributes about 88%. The DLP-TEQ generally contribute > 70% of Total-TEQ. When reporting TEQs, we recommend that the underlying congener specific concentrations are presented, TEF scheme used is clearly stated, names of compounds included are explicitly expressed, and TEQs are identified accordingly (e.g., DLP-TEQ, PCDD/F-TEQ, Total-TEQ).     

H NMR-based metabolomics investigation of Daphnia magna responses to sub-lethal exposure to arsenic,copper and lithium

Metal and metalloid contamination constitutes a major concern in aquatic ecosystems. Thus it is important to find rapid and reliable indicators of metal stress to aquatic organisms. In this study, we tested the use of ¹H nuclear magnetic resonance (NMR) – based metabolomics to examine the response of Daphnia magna neonates after a 48 h exposure to sub-lethal concentrations of arsenic (49 μg L⁻¹), copper (12.4 μg L⁻¹) or lithium (1150 μg L⁻¹). Metabolomic responses for all conditions were compared to a control using principal component analysis (PCA) and metabolites that contributed to the variation between the exposures and the control condition were identified and quantified. The PCA showed that copper and lithium exposures result in statistically significant metabolite variations from the control. Contributing to this variation was a number of amino acids such as: phenylalanine, leucine, lysine, glutamine, glycine, alanine, methionine and glutamine as well as the nucleobase uracil and osmolyte glycerophosphocholine. The similarities in metabolome changes suggest that lithium has an analogous mode of toxicity to that of copper, and may be impairing energy production and ionoregulation. The PCA also showed that arsenic exposure resulted in a metabolic shift in comparison to the control population but this change was not statistically significant. However, significant changes in specific metabolites such as alanine and lysine were observed, suggesting that energy metabolism is indeed disrupted. This research demonstrates that ¹H NMR-based metabolomics is a viable platform for discerning metabolomic changes and mode of toxicity of D. magna in response to metal stressors in the environment.     

Impact of soil water regime on degradation and plant uptake behaviour of the herbicide isoproturon in different soil types

The environmental fate of the worldwide used herbicide isoproturon was studied in four different, undisturbed lysimeters in the temperate zone of Middle Europe. To exclude climatic effects due to location, soils were collected at different regions in southern Germany and analyzed at a lysimeter station under identical environmental conditions. ¹⁴C-isoproturon mineralization varied between 2.59% and 57.95% in the different soils. Barley plants grown on these lysimeters accumulated ¹⁴C-pesticide residues from soil in partially high amounts and emitted ¹⁴CO₂ in an extent between 2.01% and 13.65% of the applied ¹⁴C-pesticide. Plant uptake and ¹⁴CO₂ emissions from plants were inversely linked to the mineralization of the pesticide in the various soils: High isoproturon mineralization in soil resulted in low plant uptake whereas low isoproturon mineralization in soil resulted in high uptake of isoproturon residues in crop plants and high ¹⁴CO₂ emission from plant surfaces. The soil water regime was identified as an essential factor that regulates degradation and plant uptake of isoproturon whereby the intensity of the impact of this factor is strongly dependent on the soil type.     

Temporal trends in polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs, and polybrominated diphenyl ethers in Niagara river suspended sediments

Archived suspended sediment samples collected over the period 1980-2002 at Niagara-on-the-Lake in the Niagara river were analyzed to assess temporal trends in contaminants associated with historical industrial activities in the watershed (PCDDs/PCDFs, DLPCBs), compared to more modern industrial chemicals (PBDEs). The temporal trends for PCDDs/PCDFs and DLPCBs were generally similar, and showed a general trend toward decreasing concentrations, which was presumably due to implementation of control measures in the Niagara river watershed, including the remediation of hazardous waste facilities. The temporal trend in PBDEs contrasted with those of PCDDs/PCDFs and DLPCBs. Prior to 1988, PBDEs (sum of 16 congeners including deca-BDE) were generally detected at low-ppb concentrations, but showed a trend toward increasing concentrations over the period 1980-1988. After 1988, PBDE concentrations in the Niagara river showed a more rapidly increasing trend to a maximum of approximately 35 ng/g in 1995, with deca-BDE as the predominant congener detected. Samples collected over the period February 2003 to March 2004 at the head and mouth of the Niagara river were also analyzed for PBDEs; in all cases PBDE concentrations were higher at the mouth of the river at the outflow to Lake Ontario, indicating the Niagara river watershed is a source of PBDE contamination to Lake Ontario. However, PBDE concentrations in suspended sediments of the Niagara river were comparable to, or lower than, concentrations in bottom sediments in other industrialized/urbanized areas of the world. Based on these comparisons of global PBDE bottom sediment concentrations, the Niagara river watershed does not appear to be a significant local source of PBDEs to Lake Ontario, and concentrations in suspended sediments appear to be indicative of general PBDE contamination from a contamination of local, regional, and continental sources.     

Simulation of Exterior Conditions in Permanently Closed Soil Chambers by Controlling Air Flow,Soil Water Content,and Temperature

Volatile substances and gases resulting e.g. from degradation processes of chemicals in soils emit into the atmosphere and no chemical mass balance is complete without considering this path. Closed soil chambers allow the evaluation of this transfer to the atmosphere. This study deals with the influence of soil chambers with a glass plate cover on physical soil conditions in the chambers and the possibility to simulate the exterior conditions within the chambers. The water content immediately at the soil surface is an important factor for the microbial activity and the transfer of gaseous compounds to the atmosphere as well. It is monitored by specially designed water content sensors in 1 cm depth in the chamber and as control outside. Funnels with a cross section equal to the soil surface area of the chamber collect the rain water and channel it into the soil chamber. This results in soil water content in the chambers very similar to that outside. For the purpose of analysing ¹⁴CO₂ and volatile ¹⁴C-compounds, air is permanently pumped through the chamber. In order to simulate natural conditions, the wind speed is measured 1 cm above the soil surface outside the chambers. A control circuit adjusts the air flow through the chamber to a value corresponding to the wind speed outside. Temperature measurements in 1 cm depth verify that there is no significant difference between the soil chamber and the control outside.     

The acceptability of CO2 capture and storage (CCS) in Europe: An assessment of the key determining factors: Part 2. The social acceptability of CCS and the wider impacts and repercussions of its implementation

In Part 1, we presented the findings of the EU ACCSEPT project (2006–2007) with regards to scientific, technical, legal and economic issues. In Part 2, we present the analysis of social acceptability on the part of both the lay public and stakeholders. We examine the acceptability of CO₂ capture and geological storage (CCS) within the Clean Development Mechanism (CDM) of the Kyoto Protocol. The debate over the inclusion of CCS within the CDM is caught-up in a set of complex debates that are partly technical and partly political and, therefore, difficult, and time-consuming, to resolve. We explore concerns that support for CCS will detract from support for other low-carbon energy sources. We can find no evidence that support for CCS is currently detracting from support for renewable energy sources, though it is probably too early to detect such an effect. Efforts at understanding, engaging with, and communicating to, the lay public and wider stakeholder community (not just business) in Europe are currently weak and inadequate, despite well-meaning statements from governments and industry.     

Occurrence and sources of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in surficial sediments of Lakes Superior and Huron

Concentrations and congener profile patterns of 2378-substituted PCDD/Fs and DLPCBs in offshore, nearshore and tributary sediments of Lakes Superior and Huron are reported, and spatial trends and source contributions assessed. PCDD/F concentrations ranged from 5 to 18 000 pg/g dw (Lake Superior) and 3 to 6100 pg/g dw (Lake Huron); DLPCBs ranged from 9 to 11 000 pg/g dw (Lake Superior) and 9 to 27 000 pg/g dw (Lake Huron). Our analysis indicated atmospheric deposition is a primary source to depositional areas of both lakes; however, greater PCDD/F and DLPCB concentrations were observed at several nearshore and tributary sites, and were attributed to corresponding land use in the watershed. Statistical analysis and pattern comparison suggested that industrial inputs mainly associated with wood treatment plants, pulp and paper mills, mining operations, and chlorine-based chemical manufacturing also contributed to contamination by PCDD/Fs and DLPCBs in certain nearshore and offshore areas of Lakes Superior and Huron.     

Evidence for selection in response to radiation exposure: Pinus sylvestris in the Chernobyl exclusion zone

Changes of genetic structures due to viability selection are likely to occur in populations exposed to rapidly and extremely changing environmental conditions after catastrophic events. However, very little is known about the extent of selective responses and in particular the proportion of the genome involved in putatively adaptive reactions for non-model plants. We used amplified fragment length polymorphisms (AFLPs) in order to investigate genetic differences between pine (Pinus sylvestris) trees which were partially exposed to extreme environmental conditions. Genetic variation patterns of pines exposed to high radiation in the Chernobyl exclusion zone with or without phenotypic stress symptoms were compared to control trees with a similar origin. Six percent of the investigated loci (15 of 222 loci) were identified as candidates for selective responses. Moderate differentiation was observed between groups of trees showing either weak or strong phenotypic responses to high radiation levels.     

Effect of fluctuating soil humidity on in situ bioavailability and degradation of atrazine

This study elucidates the effect of fluctuating soil moisture on the co-metabolic degradation of atrazine (6-chloro-N²-ethyl-N⁴-isopropyl-1,3,5-triazine-2,4-diamine) in soil. Degradation experiments with ¹⁴C-ring-labelled atrazine were carried out at (i) constant (CH) and (ii) fluctuating soil humidity (FH). Temperature was kept constant in all experiments. Experiments under constant soil moisture conditions were conducted at a water potential of −15 kPa and the sets which were run under fluctuating soil moisture conditions were subjected to eight drying-rewetting cycles where they were dried to a water potential of around −200 kPa and rewetted to −15 kPa. Mineralization was monitored continuously over a period of 56 d. Every two weeks the pesticide residues in soil pore water (PW), the methanol-extractable pesticide residues, the non-extractable residues (NER), and the total cell counts were determined. In the soil with FH conditions, mineralization of atrazine as well as the formation of the intermediate product deisopropyl-2-hydroxyatrazine was increased compared to the soil with constant humidity. In general, we found a significant correlation between the formation of this metabolite and atrazine mineralization. The cell counts were not different in the two experimental variants. These results indicate that the microbial activity was not a limiting factor but the mineralization of atrazine was essentially controlled by the bioavailability of the parent compound and the degradation product deisopropyl-2-hydroxyatrazine.     

Mineralization and Transfer Processes of <Superscript>14</Superscript>C-labeled Pesticides in Outdoor Lysimeters

A recently designed two-chamber-lysimeter-test-system allows the detailed investigation of degradation, transport and transfer processes of ¹⁴C-labeled substances in soil–plant–atmosphere-systems under outdoor conditions. With this test system it is feasible to distinguish between ¹⁴C-emissions from soil surfaces and ¹⁴C-emissions from plant surfaces in soil monoliths under real environmental conditions. Special soil humidity sensors allow the measurement of soil water content near to the soil surface, in 1 and 5 cm depth. The behavior of organic chemicals can be followed for a whole vegetation period and a mass balance for the applied chemical can be established. Some selected results of the herbicides isoproturon and glyphosate – using the two-chamber-lysimeter-test-system – are presented to demonstrate its applicability for the identification and quantification of the processes that govern pesticide behavior in soil–plant-systems. Mineralization of ¹⁴C-isoproturon was very different in four different soils; the mineralization capacity of the soils ranged from 2 to 60%. Leaching of isoproturon in general was very low, but depending on the soil type and environmental conditions isoproturon and its metabolites could be leached via preferential flow, especially shortly after application. For the herbicide ¹⁴C-glyphosate no accumulation of residues in the soil and no leaching of the residues to deeper soil layers could be observed after three applications. Glyphosate was rapidly degraded to AMPA in the soil. Glyphosate and AMPA were accumulated in soy bean nodules.