Applying metabolic fingerprinting to ecology: The use of Fourier-transform infrared spectroscopy for the rapid screening of plant responses to N deposition

The potential for metabolic fingerprinting via Fourier-transform infrared (FT-IR) spectroscopy to provide a novel approach for the detection of plant biochemical responses to N deposition is examined. An example of spectral analysis using shoot samples taken from an open top chamber (OTC) experiment simulating wet ammonium deposition is given. Sample preparation involved oven drying and homogenisation via mill grinding. Slurries of a consistent dilution were then prepared prior to FT-IR analysis. Spectra from control, 8 and 16 kg N ha^–1 yr^–1 treatments were then subjected to cross-validated discriminant function analysis. Ordination diagrams showed clear separation between the three N treatments examined. The potential for using Calluna vulgaris (L.) Hull as a bioindicator of N deposition is further evident from these results. The results also clearly demonstrate the power of FT-IR in discriminating between subtle phenotypic alterations in overall plant biochemistry as affected by ammonium pollution.     

HISTORICAL TRENDS IN SEDIMENTATION RATES AND SEDIMENT PROVENANCE,FAIRFIELD LAKE,WESTERN NORTH CAROLINA1

Sedimentation rates and sediment provenance were examined for lacustrine sediments deposited in Fairfield Lake, western North Carolina, during the past 111 years. Stratigraphic, radionuclide, and cartographic data indicate that sedimentation rates have increased several fold during the past three decades in response to localized development. The magnitude of increased sedimentation was surprising given limited development within the basin: 0.12 to 0.68 buildings/ha in 2000 in those parts directly delivering sediment to the dated cores. Thus, the analysis illustrates the potential sensitivity of watersheds in the southern Appalachians to changes in land cover. An approach that combined geochemical fingerprinting with sediment mixing models was subsequently evaluated to determine its ability to accurately estimate the contribution of sediment from (1) major bedrock formations that underlie the watershed and (2) potential sources associated with four land cover categories. Sediment sources in both analyses proved difficult to geochemically fingerprint to greater than 90 percent accuracy using data on acid‐soluble metals and selected isotopes of lead (Pb). The relative contributions of sediment from delineated sources, estimated by the mixing models, generally corresponded with known temporal and spatial patterns of land cover. However, the models were plagued by two significant problems — the chemical alteration of sediments as they were transported through upland streams to depositional sites within the lake and the loss of elemental mass. Thus, future investigations using the fingerprinting approach in this area of intense weathering, and presumably others, will need to modify the existing methods to more accurately elucidate changes in sediment provenance related to development.     

溢油鉴别数字化判定在船舶油污事故调查中的应用

本文以一起船舶油污事故的溢油源调查为例,简述了重复性限法、t检验法两种方法的判定原则及判定流程,具体介绍了两种方法在船舶油污事故溢油源鉴定中的应用。应用结果表明,重复性限法、t检验法是两种值得在船舶溢油事故鉴定中推广应用的判别方法,诊断比值的准确性是影响两种判定方法应用的一个重要因素。     

Backwater Confluences of the Ohio River: Organic and Inorganic Fingerprints Explain Sediment Dynamics in Wetlands and Marinas

In the Ohio River (OR), backwater confluence sedimentation dynamics are understudied, however, these river features are expected to be influential on the system’s ecological and economic function when integrated along the river’s length. In the following paper, we test the efficacy of organic and inorganic tracers for sediment fingerprinting in backwater confluences; we use fingerprinting results to evidence sediment dynamics controlling deposition patterns in confluences used for wetland and marina functions; and we quantify the spatial extent of tributary drainages with wetland and marina features in OR confluences. Both organic and inorganic tracers statistically differentiate sediment from stream and river end‐members. Carbon and nitrogen stable isotopes produce greater uncertainty in fingerprinting results than inorganic elemental tracers. Uncertainty analysis of the nonconservative tracer term in the organic matter fingerprinting application estimates an apparent enrichment of the carbon stable isotopes during instream residence, and the nonconservativeness is quantified with a statistical approach unique to the fingerprinting literature. Wetland and marina features in OR confluences impact 42% and 11% of tributary drainage areas, respectively. Sediment dynamics show wetland and marina confluences experience deposition from river backwaters with longitudinally linear and nonlinear patterns, respectively, from sediment sources.     

Supercritical Fluid Extraction for Forensic Analysis of Hydrocarbons in Soil

Supercritical fluid extraction (SFE) was investigated to evaluate its potential for obtaining high quality chromatographic fingerprints from soils encountered in environmental investigations. While the volatile and semivolatile fractions of light nonaqueous phase liquid (LNAPL) samples can be “fingerprinted” in a single chromatographic run, it is commonly not possible to obtain samples of LNAPL in the locations of interest. For this and other reasons, it was desirable to develop this method (SFE) of soil extraction, which allows chromatographic fingerprinting of the same quality routinely obtained with LNAPL so that environmental forensic investigations could be extended to areas beyond those containing LNAPL in monitoring wells. In this study, SFE was compared to conventional dichloromethane extraction. Both artificially spiked soil and soil from petroleum release sites were tested. Since water can be a problem when using the SFE method, particular attention was given to handling soils with high moisture contents. The SFE extracts showed excellent retention of low molecular components, including pentanes. Gas chromatography of SFE extracts yielded molecular distributions that showed no significant bias toward either low or high molecular weight components. These results show that SFE can be used to obtain an unbiased, single-run chromatographic “fingerprint” of both volatile and semivolatile hydrocarbons in contaminated soil samples.     

Fingerprinting of Gasoline and Coal Tar NAPL Volatile Hydrocarbons Dissolved in Groundwater

Accidental spills and chronic leaks of fuel oil or other hydrocarbon material (e.g., coal tar) often result in subsurface accumulation of nonaqueous phase liquid (NAPL), which can be a subsequent source of contamination in groundwater. Linking hydrocarbons in groundwater to a source NAPL has been difficult when using standard target analytes (e.g., BTEX) because of differences in partitioning properties of the analytes between the source NAPL and groundwater. Because aqueous solubility is predicted to be the controlling influence in the partitioning of hydrocarbons from NAPL to groundwater, a solubility-based approach to matching dissolved hydrocarbons in groundwater to their source NAPL has been developed and validated for two sites with commonly encountered types of NAPL contamination. Specifically, a gasoline LNAPL and a coal tar DNAPL from two separate sites (West Virginia and California) and groundwater interfaced with these NAPLs were analyzed for approximately 50 gasoline-range hydrocarbons consisting of paraffin, isoparaffin, (mono-) aromatic, naphthene, and olefin compounds (PIANO). Solubility characteristics of selected alkyl aromatic hydrocarbons from the PIANO analysis were used to identify a set of diagnostic hydrocarbons, expressed as hydrocarbon ratios, which were found to be useful in distinguishing the source(s) of hydrocarbons in groundwater. At the West Virginia site, the diagnostic ratios in a downgradient groundwater sample were similar to those of a gasoline NAPL at that site, indicating the source of hydrocarbons to the groundwater was the upgradient gasoline NAPL. The diagnostic ratios of the groundwater in contact with the gasoline NAPL and the remote groundwater were also similar, providing evidence that the diagnostic ratios were retained during transport in the aquifer. At the California site, diagnostic ratios in a cross-gradient groundwater sample differed from those of the coal tar NAPL at that site, indicating that the remote groundwater hydrocarbons did not originate from the coal tar contamination. Environmental factors such as selective degradation of specific isomers and various geological conditions (e.g., soil mineralogy, and organic content) may confound the application of this solubility-based fingerprinting approach. Thus, it is recommended that multiple diagnostic pairs be simultaneously evaluated when considering this fingerprinting approach for specific sites and product types.     

Tracing the sources of refractory dissolved organic matter in a large artificial lake using multiple analytical tools

Structural and chemical characteristics of refractory dissolved organic matter (RDOM) from seven different sources (algae, leaf litter, reed, compost, field soil, paddy water, treated sewage) were examined using multiple analytical tools, and they were compared with those of RDOM in a large artificial lake (Lake Paldang, Korea). Treated sewage, paddy water, and field soil were distinguished from the other sources investigated by their relatively low specific UV absorbance (SUVA) values and more pronounced fulvic-like versus humic-like fluorescence of the RDOM samples. Microbial derived RDOM from algae and treated sewage showed relatively low apparent molecular weight and a higher fraction of hydrophilic bases relative to the total hydrophilic fraction. For the biopolymer types, the presence of polyhydroxy aromatics with the high abundance of proteins was observed only for vascular plant-based RDOM (i.e., leaf litter and reed). Molecular weight values exhibited positive correlations with the SUVA and the hydrophobic content among the different RDOM, suggesting that hydrophobic and condensed aromatic structures may be the main components of high molecular weight RDOM. Principal component analysis revealed that approximately 77% of the variance in the RDOM characteristics might be explained by the source difference (i.e., terrestrial and microbial derived) and a tendency of further microbial transformation. Combined results demonstrated that the properties of the lake RDOM were largely affected by the upstream sources of field soil, paddy water, and treated sewage, which are characterized by low molecular weight UV-absorbing and non-aromatic structures with relatively high resistance to further degradation.     

Extra-pair paternity in willow ptarmigan broods: measuring costs of polygyny to males

Willow ptarmigan are one of only three monogamous grouse species in North America. However, in some populations between 5 and 20% of individuals pair polygynously. It has been suggested that monogamy may be maintained by the high cost of polygyny to males. We have used DNA fingerprinting to assess the actual reproductive success of both monogamous and polygynous adults. We determined whether or not the putative parents were the biological parents of the chicks from 38 broods. Of these clutches 30 were from monogamous matings, and 8 were from bigamous matings. Of the 207 chicks from monogamous matings 96% were within-pair offspring, compared to 67% of the 49 chicks from bigamous matings. All extra-pair offspring chicks resulted from extra-pair fertilizations (EPFs), and there were no instances of intraspecific nest parasitism. Mate guarding by monogamous males seems to be a highly effective method for maintaining genetic monogamy, as the only cases in which EPFs occurred were when the resident female left the territory for a few days or when a second female visited the territory. Our results support the notion that certainty of parentage may be one factor constraining willow ptarmigan males to be monogamous.     

Fingerprinting Global Climate Change and Forest Management Within Rhizosphere Carbon and Nutrient Cycling Processes

As one of the two Principal Subject Editors for ESPR Subject Area 1 'Terrestrial Ecology and Biology / Soil and Sediments: Toxicology-related Subjects' (see pp 287-293), the senior author and his colleague, Dr Chen, present an example of sub-category 4 'Environmental studies of pesticides, air pollution, and management strategies for forestry and plant ecosystems'. Thereby, they inform the ESPR community about the new Australian research project concerning the fingerprints of global climate change (GCC) and forest management on rhizosphere carbon and nutrient cycling and, subsequently, present an overview on the GCC and forest management fingerprints.     

Extra-pair paternity and the opportunity for sexual selection in a socially monogamous bird (Dendroica petechia)

We used multi-locus DNA fingerprinting to characterise the genetic mating system of the socially monogamous yellow warbler (Dendroica petechia). Over 2 years there were no instances of brood parasitism, but 59% of families (n = 90) contained extrapair sired young and 37% of offspring (n = 355) were of extra-pair paternity. Most hypotheses for extra-pair mating in monogamous species assume a paternity benefit to extra-pair sires, and focus on the benefit(s) to females. However, the assumption of male benefit has been little tested. Among yellow warblers, known extra-pair sires were just as likely to be cuckolded as any male in the population, and there was at least one reciprocal exchange of extra-pair paternity. Nevertheless, among known extra-pair sires, the paternity gains from extra-pair paternity were, on average, greater than the losses in their own families. These results show there is a paternity benefit to certain males. However, the benefit is not absolute but relative and therefore more difficult to measure. The results also suggest that patterns of extra-pair fertilisation are not determined by female choice alone. Most confirmed extra-pair mates were territorial neighbours, but some resided as far as three territories apart, and greater spatial separation was implied in other cases. Thus, the opportunity for extra-pair mating is great. We estimate that as a result of extra-pair fertilisations, variance in male mating success is increased somewhere between 3-fold and 15-fold over that which would result from within-pair reproduction alone. These findings affirm the potential importance of extra-pair reproduction for sexual selection in monogamous species and they support earlier suggestions that extra-territorial forays by male yellow warblers are for the purpose of extra-pair mating.