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Leonard I Wassenaar

Publications and source records attributed to Leonard I Wassenaar.

11 recordsLinked to original sources
PubMed2006

Contrasting pathways of assimilation: stable isotope assessment of fish exposure to pulp mill effluents.

Fish are commonly used for monitoring the quality of waters receiving pulp mill effluents (PMEs). Isotopic assays of fish tissues have the potential to provide empirical evidence to link an effluent source to exposure. We show in a 45-d factorial laboratory experiment that different exposure pathways lead to isotopic signatures in fish tissue. Rainbow trout (Oncorhynchus mykiss) were exposed to 10% PME in three ways; direct exposure through addition of PME to aquaria, indirect exposure through invertebrate food consumption (Chironomus tentans cultured in 10% PME), and a combination of both exposure pathways. Of the four stable isotopes measured (delta13C, delta15N, delta34S, delta37Cl), delta13C, delta34S, and delta37Cl showed significant differences in exposed animal tissues. Delta37Cl of fish muscle tissue showed consistent differences across trophic levels and revealed contrasting pathways of PME exposure. Contrasting delta 37Cl values in C. tentans due to the presence or absence of 10% PME did not translate into delta37Cl differences in fish. Rather, delta37Cl ratios of fish muscle tissue were specifically related to 10% PME exposure in the aquaria (waterborne exposure pathway). Feasible distributions of 37Cl source contributions for observed mixture ratios confirmed that PME accounted for observed differences in delta37Cl among treatments. Direct uptake of chloride ions across gill surfaces is the most likely pathway for assimilation of PME into fish tissues. Considering the variability of PMEs and receiving environments, use of a multi-isotope approach is recommended for tracing exposure of fish. Use of 37Cl should also be considered in light of its alternative assimilation pathway.

Animals↗
PubMed2006

Decadal geochemical and isotopic trends for nitrate in a transboundary aquifer and implications for agricultural beneficial management practices.

Nitrate contamination of aquifers is a global agricultural problem. Agricultural beneficial management practices (BMPs) are often promoted as a means to reduce nitrate contamination in aquifers through producer optimized management of inorganic fertilizer and animal manure inputs. In this study, decadal trends (1991-2004) in nitrate concentrations in conjunction with 3H/3He groundwater ages and nitrate stable isotopes (delta15N, delta18O) were examined to determine whether BMPs aimed at reducing aquifer-scale nitrate contamination in the transboundary Abbotsford-Sumas aquifer were effective. A general trend of increasing nitrate concentrations in young groundwater (< approximately 5 yr) suggested that voluntary BMPs were not having a positive impact in achieving groundwater quality targets. While the stable isotope data showed that animal manure was and still is the prevalent source of nitrate in the aquifer, a recent decrease in delta15N in nitrate suggests a BMP driven shift away from animal wastes toward inorganic fertilizers. The coupling of long-term monitoring of nitrate concentrations, nitrate isotopes, and 3H/3He age dating proved to be invaluable, and they should be considered in future assessments of the impact of BMPs on nutrients in groundwaters. The findings reveal that BMPs should be better linked to groundwater nutrient monitoring programs in order to more quickly identify BMP deficiencies, and to dynamically adjust nutrient loadings to help achieve water quality objectives.

Agriculture↗
PubMed2006

Stable-hydrogen isotope heterogeneity in keratinous materials: mass spectrometry and migratory wildlife tissue subsampling strategies.

Stable-hydrogen isotope measurements (deltaD) of biological tissues have gained widespread acceptance in wildlife and forensic studies, especially in tracking geographical movements of birds and other species. Continuous-flow isotope-ratio mass spectrometry enables high-throughput deltaD analyses to be conducted on tissue samples as small as 0.15 mg, compared with conventional offline analyses that require 7-10 mg. This reduction in sample size has raised concerns regarding intra-sample hydrogen isotopic variance due to potential biological heterogeneities that could exceed interpretations of geospatial origin. To help resolve this, feathers were obtained from captive birds to examine isotopic variance expected due to sample size, location, and heterogeneity factors, and from selected wild birds to examine isotopic variance due to these and to additional dietary or location changes during feather growth. Captive bird feathers were sub-sampled along the vane on either side of a single feather at masses of 0.25, 0.35, 0.45, 0.6, 1.0 and 2.0 mg, and along the rachis. The results showed consistency of feather deltaD measurements across a wide range of sample masses. Within-feather deltaD isotopic variance for captive and some wild birds was as low as +/-3 per thousand for vane material, which corresponds to a geospatial resolution of about 1 degree of latitude in central North America. Intra-sample variance for the rachis was +/-5 per thousand, with lower deltaD values for both wild and captive birds. However, given the extraordinary intra-feather deltaD variance observed in some wild species, we recommend researchers first carefully assess the degree of intra- and inter-sample hydrogen isotopic variation in the selected tissue growth period for the species of interest before geospatial interpretations of origin are attempted.

Animal Migration↗
PubMed2005

Global application of stable hydrogen and oxygen isotopes to wildlife forensics.

Stable isotopes are being increasingly used in wildlife forensics as means of determining the origin and movement of animals. The heavy isotope content of precipitated water and snow (deltaD(p), delta(18)O(p)) varies widely and systematically across the globe, providing a label that is incorporated through diet into animal tissue. As a result, these isotopes are potentially ideal tracers of geographic origin. The hydrogen and oxygen isotope tracer method has excellent potential where (1) spatial variation of precipitation isotopes exist, and (2) strong, mechanistic relationships link precipitation and isotope ratios in biological tissue. Here, we present a method for interpolation of precipitation isotope values and use it to create global basemaps of growing-season (GS) and mean annual (MA) deltaD(p) and delta(18)O(p). The use of these maps for forensic application is demonstrated using previously published isotope data for bird feathers (deltaD(f)) in North America and Europe. The precipitation maps show that the greatest potential for applying hydrogen and oxygen isotope forensics exists in mid- to high-latitude continental regions, where strong spatial isotope gradients exist. We demonstrate that deltaD(f)/deltaD(p) relationships have significant predictive power both in North America and Europe, and show how zones of confidence for the assignment of origin can be described using these predictive relationships. Our analysis focuses on wildlife forensics, but the maps and approaches presented here will be equally applicable to criminal forensic studies involving biological materials. These maps are available in GIS format at http://www.waterisotopes.org.

Animals↗
PubMed2005

Effects of selected pharmaceuticals on riverine biofilm communities.

Although pharmaceutical and therapeutic products are widely found in the natural environment, there is limited understanding of their ecological effects. Here we used rotating annular bioreactors to assess the impact of 10 microg.L(-1) of the selected pharmaceuticals ibuprofen, carbamazepine, furosemide, and caffeine on riverine biofilms. After 8 weeks of development, community structure was assessed using in situ microscopic analyses, fluor-conjugated lectin binding, standard plate counts, fluorescent in situ hybridization, carbon utilization spectra, and stable carbon isotope analyses. The biofilm communities varied markedly in architecture although only caffeine treated biofilms were significantly thicker. Cyanobacteria were suppressed by all 4 compounds, whereas the nitrogen containing caffeine, furosemide, and carbamazepine increased algal biomass. Ibuprofen and carbamazepine reduced bacterial biomass, while caffeine and furosemide increased it. Exopolymer content and composition of the biofilms was also influenced. Significant positive and negative effects were observed in carbon utilization spectra. In situ hybridization analyses indicated all treatments significantly decreased the gamma-proteobacterial populations and increased beta-proteobacteria. Ibuprofen in particular increased the alpha-proteobacteria, beta-proteobacteria, cytophaga-flavobacteria, and SRB385 probe positive populations. Caffeine and carbamazepine additions resulted in significant increases in the high GC354c and low GC69a probe positive cells. Live-dead analyses of the biofilms indicated that all treatments influenced the ratio of live-to-dead cells with controls having a ratio of 2.4, carbamazepine and ibuprofen being 3.2 and 3.5, respectively, and furosemide and caffeine being 1.9 and 1.7, respectively. Stable isotope analyses of the biofilms indicated delta 13C values shifted to more negative values relative to control biofilms. This shift may be consistent with proportional loss of cyanobacteria and relative increase in algal biomass rather than incorporation of pharmaceutical carbon into microbial biofilm. Thus, at 10 microg.L(-1) levels pharmaceuticals exhibit both nutrient-like and toxic effects on riverine microbial communities.

Bacteria↗
PubMed2004

On-line technique for the determination of the delta37Cl of inorganic and total organic Cl in environmental samples.

Here we describe an on-line method for measuring delta(37)Cl values of chloride bearing salts, waters, and organic materials using multicollector continuous-flow isotope ratio mass spectrometry (CF-IRMS). Pure AgCl quantitatively derived from total Cl in water, inorganic Cl salts, and biological samples was reacted with iodomethane in evacuated 10-mL stopper sealed glass vials to produce methyl chloride gas. A GV Instruments Multicollector CF-IRMS with CH(3)Cl optimized collector geometry was modified to accommodate a headspace single-sample gas injection port prior to a GC column. The GC column was a 2-m Porapak-Q packed column held at 160 degrees C. The resolved sample CH(3)Cl was introduced to the IRMS source in a helium stream via an open split. delta(37)Cl values were calculated by measurement of CH(3)Cl at m/z 52/50 and by comparison to a reference pulse of CH(3)Cl calibrated to standard mean ocean chloride. Sample CH(3)Cl analysis time was approximately 6 min. Injections of 40 microL of pure CH(3)Cl gas yielded a repeatability (+/-SD) of +/-0.06 per thousand for delta(37)Cl (n = 10). Combined GC and IRMS source linearity for CH(3)Cl was <0.2 per thousand/nA (V) peak height. External repeatability, based on processing of seawater and NaCl reference solutions, was better than +/-0.08 per thousand. The smallest sample for delta(37)Cl analysis by this method was approximately 0.2 micromol of Cl. Selected results from a river basin and biological samples study illustrate the potential of on-line chlorine isotope assays in environmental pollution studies.

Journal Article↗
PubMed2004

Using stable hydrogen and oxygen isotope measurements of feathers to infer geographical origins of migrating European birds.

Successful application of stable-hydrogen isotope measurements (deltaDf) of feathers to track origins of migratory birds and other wildlife requires a fundamental understanding of the correlation between deltaDf and deuterium patterns in rainfall (deltaDp) over continental scales. A strong correlation between deltaDp and deltaDf has been confirmed for birds and insects in North America, but not yet for other continents. Here, we compare deltaDf data from resident European birds to new deltaDp basemaps for Europe. Three maps, representing growing-season and mean annual deltaDp estimates from an elevation-explicit, detrended interpolation model and growing-season deltaDp estimates from simple Kriging, all indicate that strong isotope gradients occur across Europe with a general depletion occurring in a northeast direction. The feather data, representing 141 individuals of 25 avian species from 38 sites, ranged from -131 to -38 per thousand. Regression analysis showed that strong correlations existed between both mean annual and growing-season deltaDp estimated by detrended interpolation and deltaDf of non-aquatic and non-corvid birds (r2=0.66 and 0.65, respectively). We also examined mean annual and growing-season delta18Op vs. delta18Of for our samples. Both oxygen regressions were similar (r2=0.56 and 0.57, respectively) but poorer than for deuterium. Our study reveals that deltaD measurements of feathers from migratory birds in Europe may be used to track their origin and movements, and so provide a powerful investigative tool for avian migration research in Europe.

Animals↗
PubMed2004

Transport and geochemical controls on the distribution of solutes and stable isotopes in a thick clay-rich till aquitard, Canada.

A comprehensive understanding of the transport and geochemical processes controlling solutes in clay-rich aquitard confining units is needed to accurately predict the long-term migration of contaminants into the subsurface. To this end, the geochemical and stable isotopic composition of porewaters in the upper 22 m of a thick, unoxidized and nonfractured clay-rich, till aquitard (Sutherland Group) was examined in detail. The aquitard is overlain by about 8 m of oxidized and fractured till (Floral Fm). Concentrations of TDS, SO4(2-), HCO3-, Cl-, Na+, Mg2+, Ca2+ and porewater deuterium were greater in the Floral Fm and decreased with depth through the aquitard. The elevated and seasonably variable solute concentrations in the oxidized Floral Fm were attributed to geochemical weathering and dynamic water movement through fractures. Good fits between measured delta2H, TDS, SO4(2-), Cl- and HCO3- profiles through the aquitard and simulated solute transport profiles were obtained by diffusion (without advection) with transport times of 4-6 ka. The deficiency of geochemical reactions affecting HCO3- and SO4(2-) in the aquitard was supported by delta13C(DIC) and delta34S(SO4) analyses. Geochemical and isotope mass balance modelling (NETPATH) indicated that diffusive mixing with minor calcite dissolution and ion exchange could account for the distribution of Na+, Ca2+ and Mg2+ in the aquitard. Results of this study further suggested that microbiological activity in the aquitard was limited. With minor exceptions, the solute and isotopic profiles, their transport and the controlling geochemical reactions in the Sutherland are similar to those determined at another clay-rich till aquitard, 160 km south of this site, suggesting that geochemical and biological processes in some clay-rich aquitards may have a minimal effect on the migration of dissolved constituents.

Aluminum Silicates↗
PubMed2004

Chemical and carbon isotopic composition of dissolved organic carbon in a regional confined methanogenic aquifer.

This study demonstrates the advantage of a combined use of chemical and isotopic tools to understand the dissolved organic carbon (DOC) cycle in a regional confined methanogenic aquifer. DOC concentration and carbon isotopic data demonstrate that the soil zone is a primary carbon source of groundwater DOC in areas close to recharge zones. An in-situ DOC source linked to organic rich sediments present in the aquifer matrix is controlling the DOC pool in the central part of the groundwater flow system. DOC fractions, 13C-NMR on fulvic acids and 14C data on DOC and CH4 support the hypothesis that the in-situ DOC source is a terrestrial organic matter and discard the Ordovician bedrock as a source of DOC.

Carbon↗
PubMed2003

Microbial respiration and diffusive transport of O2, 16O2, and 18O15O in unsaturated soils and geologic sediments.

Molecular oxygen (O2) in unsaturated geologic sediments plays an important role in soil respiration, biodegradation of organic contaminants, metal oxidation, and global oxygen and carbon cycling, yet little is known about oxygen isotope fractionation during the consumption and transport of O2 in unsaturated zones. We used a laboratory kinetic cell technique to quantify isotope fractionation due to respiration and a numerical model to quantify both consumptive and diffusive fractionation of O2 isotopes at a field site comprised of unsaturated lacustrine sandy materials. The combined use of laboratory-based kinetic cell experiments and field-based isotope transport modeling provided an effective tool to characterize microbial respiration in unsaturated media. Based on results from the closed-system kinetic cells, O2 consumption and isotope fractionation were attributed to the alternative cyanide-resistant respiration pathway. At the field site, the modeled depth profiles for O2 and delta18O matched the measured in situ data and confirmed that the consumption of O2 was via the alternative respiration pathway. If the cyanide-resistant respiration pathway is indeed widespread in soils, its high oxygen isotope enrichment factor could help to explain the discrepancy between the predicted present-day Dole effect (+20.8/1000) and the observed Dole effect (+23.5/1000). Thus, further soil O2 isotope studies are needed to better characterize and model the fractionation of oxygen isotopes during subsurface respiration and the potential impact on the isotopic content of atmospheric O2.

Biodegradation, Environmental↗