Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations

Gas chromatography-isotope ratio mass spectrometry (GC-IRMS) has made it possible to analyze natural stable isotope ratios (e.g., (13)C/(12)C, (15)N/(14)N, (2)H/(1)H) of individual organic contaminants in environmental samples. They may be used as fingerprints to infer contamination sources, and may demonstrate, and even quantify, the occurrence of natural contaminant transformation by the enrichment of heavy isotopes that arises from degradation-induced isotope fractionation. This review highlights an additional powerful feature of stable isotope fractionation: the study of environmental transformation mechanisms. Isotope effects reflect the energy difference of isotopologues (i.e., molecules carrying a light versus a heavy isotope in a particular molecular position) when moving from reactant to transition state. Measuring isotope fractionation, therefore, essentially allows a glimpse at transition states! It is shown how such position-specific isotope effects are "diluted out" in the compound average measured by GC-IRMS, and how a careful evaluation in mechanistic scenarios and by dual isotope plots can recover the underlying mechanistic information. The mathematical framework for multistep isotope fractionation in environmental transformations is reviewed. Case studies demonstrate how isotope fractionation changes in the presence of mass transfer, enzymatic commitment to catalysis, multiple chemical reaction steps or limited bioavailability, and how this gives information about the individual process steps. Finally, it is discussed how isotope ratios of individual products evolve in sequential or parallel transformations, and what mechanistic insight they contain. A concluding session gives an outlook on current developments, future research directions and the potential for bridging the gap between laboratory and real world systems.     

Mechanistic Virtual Modeling: Coupling a Plant Simulation Model with a Three-dimensional Plant Architecture Component

The aim of this research is to integrate plant architectural modeling or “visualization modeling” and “mechanistic” or physiologically based modeling to describe how a real plant functions using a virtual crop. Virtual crops are life-like computer representations of crops based on individual plants and including the representation of the substrate on which the plants grow. The integration of a three-dimensional expression and the mechanistic model of plant development and growth requires the knowledge of the position of the organs along the different plant axes (the topology), their sizes, their forms, and their spatial orientation. The plant simulation model simulates the topology and organ weight or length. The superposition of spatial position and the topology produces the architecture of the plant. The association between sizes and organs creates what we refer to as the plant morphological model. Both components, the architectural model and the morphology model, are detailed in this paper. Once the integration is complete, the system produces a movie-like animation that shows the plant growing. The integrated model may simulate one or several plants growing simultaneously (in parallel). Visual capabilities make the proposed system very unique as it allows users to judge the results of the simulation the same way a farmer judges the situation of the crops in real life, by visually observing the field.     

Why the Far-Distant Future Should Be Discounted at Its Lowest Possible Rate

A critical feature of the distant future is currently unresolvable uncertainty about what will then be the appropriate rate of return on capital to use for discounting. This paper shows that there is a well-defined sense in which the “lowest possible” interest rate should be used for discounting the far-distant future part of any investment project. Some implications are discussed for evaluating long-term environmental projects or activities, like measures to mitigate the possible effects of global climate change.     

Ecology of sandy beaches in Oman

The benthic macrofauna and physical features of 10 sandy beaches along the coast of Oman were surveyed quantitatively. This is a mesotidal regime mostly subject to low to moderate wave energy but more exposed in the south. Five northern beaches are tide-dominated, with low wave energy, and their profiles consist of a berm, a steep, swash-dominated upper shore and a broad tide-dominated terrace from mid-shore downwards. They are composed of moderately sorted fine to medium sands. Southern beaches experience greater wave energy, particularly during the summer southwest monsoon, and exhibit smoother, concave profiles with fine, fairly well sorted carbonate sand. 58 species and species groups were recorded, with crustanceans, polychaetes and molluscs dominant. In general species richness was high, at least 19–25 species per beach, but dry biomass moderate to low at 26–90g/m shoreline, with one high value of 450g/m. Total abundance was moderate at 3–73×10³ organisms/m of beach. Some zonation was evident with ocypodid crabs andTylos in the supralittoral, cirolanid isopods on the upper shore and a variety of species on the lower shore. The coast of Oman appears to constitute a single zoogeographic region, but with some regional differentiation between north and south due to varying physical conditions. Thus, OmanÕs beaches are characterized by tide-dominated morphodynamics and exceptionally high species richness.     

Endocrine modulation and toxic effects of two commonly used UV screens on the aquatic invertebrates Potamopyrgus antipodarum and Lumbriculus variegatus

The two UV screens 3-benzylidene-camphor (3-BC) and 3-(4'-methylbenzylidene)-camphor (4-MBC) were tested regarding their toxicity and estrogenic activity. The Yeast Estrogen Screen (YES) and two sediment assays with the freshwater invertebrates Lumbriculus variegatus and Potamopyrgus antipodarum were performed. In the YES, both substances activated the human estrogen receptor alpha with EC50 values of 44.2 microM for 3-BC and 44.3 microM for 4-MBC, whereby 4-MBC attained only 8% of the maximal response of 17beta-estradiol. For P. antipodarum embryo production increased after exposure to both substances (EC50 of 4.60 microM 4-MBC=1.17 mg kg(-1)dw) while mortality increased at high concentrations. The reproduction of L. variegatus was decreased by 3-BC with an EC50 of 5.95 microM (=1.43 mg kg(-1)dw) and also by 4-MBC, where no EC50 could be calculated. While reproduction decreased, the worms' weight increased after exposure to 3-BC with an EC50 of 26.9 microM (=6.46 mg kg(-1) dw), hence the total biomass remained unaffected.     

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.     

Essential versus potentially toxic dietary substances: a seasonal comparison of essential fatty acids and methyl mercury concentrations in the planktonic food web

We investigated seasonal variability of essential fatty acids (EFA) and methyl mercury (MeHg) concentrations in four size categories of planktonic organisms in two coastal lakes. MeHg concentrations increased significantly with increasing plankton size and were independent of plankton taxonomy. However, total EFA increased from seston to mesozooplankton, but decreased in the cladoceran-dominated macrozooplankton size-class. Analysis of EFA patterns revealed that linoleic, alpha-linolenic, arachidonic, and eicosapentaenoic acids increased with increasing zooplankton size, but docosahexaenoic acid (DHA) in the cladoceran-dominated macrozooplankton was generally lower than in seston. This consistent pattern demonstrates that cladocerans, although bioaccumulating MeHg, convey less DHA than similar-sized copepods to their consumers. It is thus evident that fish consuming cladocerans have restricted access to DHA, yet unrestricted dietary access to MeHg. Thus, the structure of planktonic food webs clearly affects the composition of EFA and regulates dietary supply of these essential nutrients, while MeHg bioaccumulates with increasing zooplankton size.     

Vegetative buffers for fan emissions from poultry farms: 1. temperature and foliar nitrogen

This study sought to evaluate the potential of trees planted around commercial poultry farms to trap ammonia (NH(3)), the gas of greatest environmental concern to the poultry industry. Four plant species (Norway spruce, Spike hybrid poplar, Streamco willow, and hybrid willow) were planted on eight commercial farms from 2003 to 2004. Because temperature (T) can be a stressor for trees, T was monitored in 2005 with data loggers among the trees in front of the exhaust fans (11.4 to 17.7 m) and at a control distance away from the fans (48 m) during all four seasons in Pennsylvania. Norway spruce (Picea abies) foliage samples were taken in August 2005 from one turkey and two layer farms for dry matter (DM) and nitrogen (N) analysis. The two layer farms had both Norway spruce and Spike hybrid poplar (Populus deltoides x Populus nigra) plantings sampled as well allowing comparisons of species and the effect of plant location near the fans versus a control distance away. Proximity to the fans had a clear effect on spruce foliar N with greater concentrations downwind of the fans than at control distances (3.03 vs. 1.88%; P < or = 0.0005). Plant location was again a significant factor for foliar N of both poplar and spruce on the two farms with both species showing greater N adjacent to the fans compared to the controls (3.75 vs. 2.32%; P < or = 0.0001). Pooled foliar DM of both plants was also greater among those near the fans (56.17, fan vs. 44.67%, control; P < or = 0.005). Species differences were also significant showing the potential of poplar to retain greater foliar N than spruce (3.52 vs. 2.55%; P < or = 0.001) with less DM (46.00 vs. 54.83%; P < or = 0.05) in a vegetative buffer setting. The results indicated plants were not stressed by the T near exhaust fans with mean seasonal T (13.04 vs. 13.03 degrees C, respectively) not significantly different from controls. This suggested poultry house exhaust air among the trees near the fans would not result in dormancy stressors on the plants compared to controls away from the fans.     

Mercury deposition/accumulation rates in the vicinity of a lead smelter as recorded by a peat deposit

Mercury (Hg) concentration profiles and historical accumulation rates were determined in three ²¹⁰Pb-dated cores from a peat deposit in the vicinity of a lead (Pb) smelter at Příbram, Czech Republic. The Hg concentrations in peat samples ranged from 66 to 701 μg kg⁻¹. Cumulative Hg inventories from each core (for the past 150 yr) varied by a factor of 1.4 (13.6–18.5 mg Hg m⁻²), indicating variations of net Hg accumulation rate within the peat deposit. Historical changes in vegetation cover (leading to variable interception by trees) are probably responsible for this variation in space and time. The uncorrected Hg accumulation rates peaked between the 1960s and 1980s (up to 226 μg m⁻² yr⁻¹). Recent findings show that Hg records from peat tend to overestimate historical levels of Hg deposition. Therefore we used the mass loss compensation factor (MLCF) to normalize Hg accumulation rates. These corrected Hg accumulation rates were significantly lower (maximum 129 μg m⁻² yr⁻¹) and better corresponded to changes in historical smelter emissions, which were highest in the 1960s. The agreement between the corrected Hg accumulation rates in the uppermost peat sections (2–38 μg m⁻² yr⁻¹) and biomonitoring of atmospheric deposition by mosses in several recent years (4.7–34.4 μg m⁻² yr⁻¹) shows the usefulness of MLCF application on Hg accumulation in peat archives. However, the MLCF correction was unsuitable for Pb. The recent Pb deposition rates obtained by an independent biomonitoring study using mosses (0.5–127 mg m⁻² yr⁻¹) were better correlated with net Pb accumulation rates recorded in peat (7–145 mg m⁻² yr⁻¹) than with corrected rates obtained by the MLCF approach (1–28 mg m⁻² yr⁻¹).     

ELISA detection of multixenobiotic resistance transporter induction in indigenous freshwater Chironomidae larvae (Diptera): A biomarker calibration step for in situ monitoring of xenobiotic exposure

A new simple and sensitive method to distinguish chemically polluted from unpolluted situations in freshwater ecosystems is reported. For this purpose, Chironomus gr thumni larvae were collected from a polluted urban river downstream a sewage treatment plant. For the first time, ELISA assay was used to semi-quantify the multixenobiotic resistance transporters (MXR) in these small pertinent bioindicators. The use of samples immediately fixed in the field gives a delay to isolate larvae and allows multi-sampling along a longitudinal transect in a river at a given time. Results exhibit an induction of MXR proteins in larvae from the polluted river and a deinduction in larvae maintained 11days in unpolluted water. They show new evidences to use midge larvae in biomonitoring environmental programs. They answer to first biomarker calibration steps for the ongoing development of MXR transporters as a detection tool of xenobiotic impacts on bioindicator invertebrates in their freshwater habitats.