The application of analytical techniques to the understanding of chemical processes occurring in the atmosphere†

The science of atmospheric chemistry has expanded enormously over the last decade. In the stratosphere it has become apparent that small traces of a number of gases can perturb the earth's ozone layer. In the troposphere it is now realised that a general oxidation process is occurring which involves several free radicals and a large number of stable gaseous molecules containing the elements H, C, N, O, S, P, F, Cl, Br and I. In areas close to centres of large population this leads to the phenomenon of photochemical smog and in more remote areas it leads to excess acidity in rainwater.

In order to gain information on these problems and understand the underlying causes, many new analytical techniques have been developed. These are based mostly on chemilu‐minescence, laser spectroscopy, gas chromatography and mass spectrometry. Some examples of the application of these techniques will be given with emphasis placed on the role of GC/MS (gas chromatography combined with mass spectrometry).     

Identification and apportionment of sources of lead in human tissue

A brief review of the use of stable lead isotope ratio measurements to identify and apportion sources of lead in human tissue is followed by examples of the use of inductively coupled plasma source mass spectrometry for such studies. Inductively coupled plasma source mass spectrometry (ICP-MS) has only recently been used for measurements of coupled ratios in body tissues and fluids and in environmental sources of lead. Generally, the inaccuracy of these measurements is about −0.2% and the imprecision less than 0.5%. This analytical performance is sufficient to detect the much larger changes in²⁰⁶Pb:²⁰⁷Pb ratios of −2% or higher, seen in environmental lead exposure and in childhood lead poisoning. Measurements of lead isotope ratios by ICP-MS have been used to identify specific sources of childhood lead poisoning and to indicate the relative importance of environmental sources, such as drinking water and lead from petrol. Populations in the United Kingdom with low lead uptake usually have²⁰⁶:Pb²⁰⁷Pb ratios in body tissues within the range 1.13 ± 0.01. Significant deviations from this range have been seen in response to increased uptake from lead in: drinking water in parts of Scotland (source ratio ∼1.18 and petrol lead in inner London (source ratio ∼1.07). The dominant source for some Scottish subjects with high concentrations of lead in blood or in teeth was water, which contributed approximately 60% to body lead. Petrol lead was shown to be a significant contributor (30–40%) to the body lead of inner London children.     

A Bayesian framework for stable isotope mixing models

Stable isotope sourcing is used to estimate proportional contributions of sources to a mixture, such as in the analysis of animal diets and plant nutrient use. Statistical methods for inference on the diet proportions using stable isotopes have focused on the linear mixing model. Existing frequentist methods provide inferences when the diet proportion vector can be uniquely solved for in terms of the isotope ratios. Bayesian methods apply for arbitrary numbers of isotopes and diet sources but existing models are somewhat limited as they assume that trophic fractionation or discrimination is estimated without error or that isotope ratios are uncorrelated. We present a Bayesian model for the estimation of mean diet that accounts for uncertainty in source means and discrimination and allows correlated isotope ratios. This model is easily extended to allow the diet proportion vector to depend on covariates, such as time. Two data sets are used to illustrate the methodology. Code is available for selected analyses.     

稳定同位素在污染物溯源与示踪中的应用

由于稳定同位素在特定污染源中组成确定,且具有分析结果精确可靠、在污染物迁移与转化过程中不发生显著变化的特点,故已被广泛应用于环境污染事件的仲裁、环境污染物的来源分析与示踪研究中。介绍了稳定同位素分馏对于来源分析的影响以及稳定同位素技术在污染物溯源与示踪中识别大气多环芳烃来源、推测环境中硫和铅的来源、考察甲基叔丁基醚来源与降解过程等方面的应用进展。     

Using stable isotopes to reveal shifts in prey consumption by generalist predators.

The effectiveness of generalist predators in biological control may be diminished if increased availability of alternative prey causes individual predators to decrease their consumption of crop pests. Farming practices that enhance densities of microbidetritivores in the detrital food web can lead to increased densities of generalist predators that feed on pest species. The ability to predict the net biocontrol impact of increased predator densities depends upon knowing the extent to which individual predators may shift to detrital prey and feed less on crop pests when prey of the detritus-based food web are more abundant. We addressed this question by comparing ratios of stable isotopes of carbon (delta13C) and nitrogen (delta15N) in generalist ground predators and two types of prey (crop pests and microbidetritivores) in replicated 8 x 8 m cucurbit gardens subjected to one of two treatments: a detrital subsidy or no addition of detritus (control). Small sheet-web spiders (Linyphiidae) and small wolf spiders (Lycosidae) had delta13C values similar to those of Collembola in both the detrital and control treatments, indicating that small spiders belong primarily to the detrital food web. In control plots the larger generalist predators had delta13C values similar to those of the major insect pests, consistent with their known effectiveness as biocontrol agents. Adding detritus may have caused delta13C of one species of large wolf spider to shift toward that of the microbi-detritivores, although evidence is equivocal. In contrast, another large wolf spider displayed no shift in delta13C in the detrital treatment. Thus, stable isotopes revealed which generalist predators will likely continue to feed on pest species in the presence of greater densities of alternative prey.     

Changes in soil organic matter composition after afforestation of arable farmland in northeast China

Since the 1970s, a substantial area of arable farmland in a semi-humid area of northeast China has been planted as deciduous forests (Populus tomentosa Carr.). This study investigates the effects of afforestation on soil organic carbon (SOC) content and the chemical composition of the soil. Soil samples (Calcic chernozem) were collected from the upper 10?cm of paired arable land and secondary forests established 5 and 25 years previously. Carbon isotope analysis and pyrolysis–gas chromatography/mass spectrometry were used to determine SOC composition. The results show that (i) compared to the arable land, five years of afforestation caused a decrease in SOC and N concentration, while 25 years of afforestation resulted in an increase in SOC content; (ii) stable isotope δ¹³C analyses of the forest soils show gradual loss of crop-derived C and an accumulation of forest-derived C; and (iii) afforestation increased lignin abundance and decreased decompositional activity in the 25-year-old forest topsoil. Higher amounts of short-/mid-chain aliphatic compounds were observed in the 5-year-old forest (5–10?cm); and (iv) the arable soil contained substantially higher amounts of decomposed plant material and microbially derived substances. The results obtained suggest that long-term afforestation increases the SOC concentration, and alters the chemical composition of SOC.     

An experimental evaluation of transgenerational isotope labelling in a coral reef grouper

Transgenerational isotope labelling (TRAIL) using enriched stable isotopes provides a novel means of mass-marking marine fish larvae and estimating larval dispersal. The technique, therefore, provides a new way of addressing questions about demographic population connectivity and larval export from no-take marine protected areas. However, successful field applications must be preceded by larval rearing studies that validate the geochemical marking technique, determine appropriate concentrations and demonstrate that larvae are not adversely affected. Here, we test whether injection of enriched stable barium isotopes (¹³⁵Ba and ¹³⁷Ba) at two dose rates produces unequivocal marks on the otoliths of the coral reef grouper Epinephelus fuscoguttatus. We also assess potential negative effects on reproductive performance, egg size, condition and larval growth due to injection of adult female fish. The injection of barium isotopes at both 0.5 and 2.0 mg Ba/kg body weight into the body cavities of gravid female fish was 100% successful in the geochemical tagging of the otoliths of larvae from the first spawning after injection. The low-dose rate produced no negative effects on eggs or larvae. However, the higher dose rate of 2 mg Ba/kg produced small reductions in yolk sac area, oil globule area, standard length and head depth of pre-feeding larvae. Given the success of the 0.5 mg Ba/kg dose rate, it is clearly possible to produce a reliable mark and keep the concentration below any level that could affect larval growth or survival. Hence, enriched Ba isotope injections will provide an effective means of mass-marking grouper larvae.     

First continuous shipboard δ18O and δD measurements in sea water by diffusion sampling—cavity ring-down spectrometry

Combined measurements of salinity and the oxygen/hydrogen stable isotope composition of marine waters can characterise processes such as freshwater mixing, evaporation, precipitation and sea-ice formation. However, stable isotope data with high spatial and temporal resolution are necessary for a detailed understanding of mixed water bodies with multiple inputs. So far analysis of ??¹⁸O and ??D values in water has been a relatively expensive, laboratory-based technique requiring collection of discrete samples. This has greatly limited the scope and scale of field research that can be undertaken using stable isotope analysis. Here, we report the first continuous shipboard measurements of ??¹⁸O and ??D values in water by diffusion sampling-cavity ring-down spectrometry. Combined with continuous salinity recordings, a data set of nearly 6,000 measurements was made at 30-s intervals during a 3-day voyage through the Great Barrier Reef Lagoon. Our results show that continuous shipboard measurement of ??¹⁸O/??D values provides additional discriminatory power for assessing water mass formation processes and histories. Precise identification of river plumes within the Great Barrier Reef Lagoon was only possible because unique ??¹⁸O/??D?Csalinity relationships of individual plumes were measured at high spatial and temporal resolution. The main advantage of this new technique is the ability to collect continuous, real-time isotope data at a small fraction of the cost of traditional isotope analysi s of discrete samples. Water ??¹⁸O and ??D values measured by diffusion sampling-cavity ring-down spectrometry and laboratory-based isotope ratio mass spectrometry have similar accuracy and precision.     

Arthropod food web restoration following removal of an invasive wetland plant.

Restoration of habitats impacted by invasive plants is becoming an increasingly important tool in the management of native biodiversity, though most studies do not go beyond monitoring the abundance of particular taxonomic groups, such as the return of native vegetation. Yet, the reestablishment of trophic interactions among organisms in restored habitats is equally important if we are to monitor and understand how ecosystems recover. This study examined whether food web interactions among arthropods (as inferred by abundance of naturally occurring stable isotopes of C [delta13C] and N [delta15N]) were reestablished in the restoration of a coastal Spartina alterniflora salt marsh that had been invaded by Phragmites australis. From patterns of C and N stable isotopes we infer that trophic interactions among arthropods in the native salt marsh habitats are characterized by reliance on the dominant marsh plant Spartina as a basal resource. Herbivores such as delphacid planthoppers and mirid bugs have isotope signatures characteristic of Spartina, and predatory arthropods such as dolicopodid flies and spiders likewise have delta13C and delta15N signatures typical of Spartina-derived resources (approximately -13 per thousand and 10 per thousand, respectively). Stable isotope patterns also suggest that the invasion of Phragmites into salt marshes and displacement of Spartina significantly alter arthropod food web interactions. Arthropods in Phragmites-dominated sites have delta13C isotope values between -18 per thousand and -20 per thousand, suggesting reliance on detritus and/or benthic microalgae as basal resources and not on Phragmites, which has a delta13C approximately -26 per thousand. Since most Phragmites herbivores are either feeding internally or are rare transients from nearby Spartina, these resources do not provide significant prey resources for other arthropod consumers. Rather, predator isotope signatures in the invaded habitats indicate dependence on detritus/algae as basal resources instead of the dominant vegetation. The reestablishment of Spartina after removal of Phragmites, however, not only returned species assemblages typical of reference (uninvaded) Spartina, but stable isotope signatures suggest that the trophic interactions among the arthropods were also similar in reestablished habitats. Specifically, both herbivores and predators showed characteristic Spartina signatures, suggesting the return of the original grazer-based food web structure in the restored habitats.     

Source identification for oil-based drill cuttings on the seabed based on stable carbon isotopes

This paper demonstrates how stable carbon isotopes can be utilized to identify the source of oil-based drill cuttings discharges and estimate the time of their deposition. The base-oil used in drilling mud systems may be biodegraded by seabed microflora. Effects of such processes make it difficult to identify sources of discharges based on the oil’s molecular structure. However, the stable isotope fingerprint of the base oil may vary for each batch of base-oil. Because carbon isotopic ratios in compounds with more than ten carbons are resistant to fractionation during biodegradation, this may be used as a tool to identify the source of drill cuttings discharges.     

Response of predators to loss and fragmentation of prey habitat: a review of theory

Despite extensive empirical research and previous reviews, no clear patterns regarding the effects of habitat loss and fragmentation on predator-prey interactions have emerged. We suggest that this is because empirical researchers do not design their studies to test specific hypotheses arising from the theoretical literature. In fact, theoretical work is almost completely ignored by empirical researchers, perhaps because it may be inaccessible to them. The purpose of this paper is to review theoretical work on the effects of habitat loss and fragmentation on predator-prey interactions. We provide a summary of clear, testable theoretical predictions for empirical researchers. To test one or more of these predictions, an empiricist will need certain information on the predator and prey species of interest. This includes: (1) whether the predator is a specialist on one prey species or feeds on many kinds of prey (omnivore and generalist); (2) whether the predator is restricted to the same habitat type as the focal prey (specialist), can use a variety of habitats but has higher survival in the prey habitat (omnivore), or lives primarily outside of the focal prey's habitat (generalist); (3) whether prey-only patches have lower prey extinction rates than predator-prey patches; and (4) whether the prey emigrate at higher rates from predator-prey patches than from prey-only patches. Empiricists also need to be clear on whether they are testing a prediction about habitat loss or habitat fragmentation and need to conduct empirical studies at spatial scales appropriate for testing the theoretical prediction(s). We suggest that appropriate use of the theoretical predictions in future empirical research will resolve the apparent inconsistencies in the empirical literature on this topic.     

全球变化下有关卤代甲烷源汇的研究进展

大气中存在的卤代甲烷对臭氧层具有极强的破坏作用并参与其它气候现象，其动态变化对臭氧的恢复和地球生态系统有重要影响。文章概述了全球变化下卤代甲烷源汇的研究情况并简单探索其进一步的研究方向。几种卤代甲烷中，溴代甲烷源汇最复杂且对臭氧具有最强的破坏力，因此研究较多。已证明CH3Br的来源有：海洋、土壤、生物燃烧、陆地植物和沼泽地的释放等；CH3Br的汇包括：光化学分解、被土壤和植物吸收、在海洋中的化学和生物降解等。但事实上是已知汇远远大于已知源，且各个源汇的通量在不同研究中结果差异较大，归其原因是卤代甲烷释放与吸收机制的不确定性。虽然近几年的研究也应用了稳定同位素示踪技术，但卤代甲烷各源汇的具体贡献并不清楚。今后卤代甲烷源汇的研究重点应放在与气体产生机制最密切的地下部分即“地下生态学”对其通量的影响，而同位素技术的改进及其在痕量气体研究中的应用也将是未来的重点方向。     

Can stable isotope ratios provide for community-wide measures of trophic structure?

Stable isotope ratios (typically of carbon and nitrogen) provide one representation of an organism's trophic niche and are widely used to examine aspects of food web structure. Yet stable isotopes have not been applied to quantitatively characterize community-wide aspects of trophic structure (i.e., at the level of an entire food web). We propose quantitative metrics that can be used to this end, drawing on similar approaches from ecomorphology research. For example, the convex hull area occupied by species in delta13C-delta15N niche space is a representation of the total extent of trophic diversity within a food web, whereas mean nearest neighbor distance among all species pairs is a measure of species packing within trophic niche space. To facilitate discussion of opportunities and limitations of the metrics, we provide empirical and conceptual examples drawn from Bahamian tidal creek food webs. These examples illustrate how this methodology can be used to quantify trophic diversity and trophic redundancy in food webs, as well as to link individual species to characteristics of the food web in which they are embedded. Building from extensive applications of stable isotope ratios by ecologists, the community-wide metrics may provide a new perspective on food web structure, function, and dynamics.     

Kelp as a trophic resource for marine suspension feeders: a review of isotope-based evidence

Kelp forests are enormously productive, and they and adjacent habitats support large populations of suspension feeders. What do these suspension feeders eat? Intuitively, we might expect that kelp primary production is a key form of trophic support for these animals. Indeed, a large and growing number of studies using carbon stable isotope data, typically collected over short time periods, have asserted that detritus from kelps is an important, and in some cases the main, food source for coastal benthic suspension feeders. This view has been incorporated into several textbooks and review papers covering kelp forest ecosystems, and loss of trophic support for benthic suspension feeders is now often invoked as an ecosystem consequence of top-down or other impacts on kelp forests. More direct evidence, however, suggests that these animals mainly eat phytoplankton and, in some cases, bacteria or zooplankton. Because isotope values of pure coastal phytoplankton, uncontaminated with detritus, are difficult to obtain, present studies have largely relied on single measurements from offshore environments or from the literature, which typically reflects offshore values. We review the evidence showing that phytoplankton isotope values can, and are expected to, vary widely in coastal waters and that inshore phytoplankton may often be enriched in ¹³C compared to offshore phytoplankton. This unaccounted-for variation may have systematically biased the results of such trophic studies toward finding large contributions of kelp detritus to suspension-feeder diets. We review some key stable isotope studies and put forth evidence for alternative explanations of the isotope patterns presented. Finally, we make recommendations for future isotope studies and describe several approaches for progress in this area. New techniques, particularly flow cytometry and compound-specific stable isotope analysis, provide ways to shed light on this interesting and important ecological issue.     

The enigma of progress in denitrification research.

Humans have dramatically increased the amount of reactive nitrogen (primarily ammonium, nitrogen oxides, and organically bound N) circulating in the biosphere and atmosphere, creating a wide array of desirable products (e.g., food production) and undesirable consequences (e.g., eutrophication of aquatic ecosystems and air pollution). Only when this reactive N is converted back to the chemically unreactive dinitrogen (N2) form, do these cascading effects of elevated reactive N cease to be of concern. Among the quantitatively most important processes for converting reactive N to N2 gas is the biological process of classical denitrification, in which oxides of nitrogen are used as terminal electron acceptors in anaerobic respiration. This Invited Feature on denitrification includes a series of papers that integrate our current state of knowledge across terrestrial, freshwater, and marine systems on denitrification rates, controlling factors, and methodologies for measuring and modeling denitrification. In this paper, we present an overview of the role of denitrification within the broader N cycle, the environmental and health concerns that have resulted from human alteration of the N cycle, and a brief historical perspective on why denitrification has been so difficult to study. Despite over a century of research on denitrification and numerous recent technological advances, we still lack a comprehensive, quantitative understanding of denitrification rates and controlling factors across ecosystems. Inherent problems of measuring spatially and temporally heterogeneous N2 production under an N2-rich atmosphere account for much of this slow progress, but lack of interdisciplinary communication of research results and methodological developments has also impeded denitrification research. An integrated multidisciplinary approach to denitrification research, from upland terrestrial ecosystems, to small streams, river systems, estuaries, and continental shelf ecosystems, and to the open ocean, may yield new insights into denitrification across landscapes and waterscapes.     

Odorous volatile components in Ayus fish

Volatile components in Ayus (fish in Japan) having bad smell were analyzed by freeze‐vacuum distillation and gas chromatography/mass spectrometry to clarify the origin of the smell. Nitrogen heterocyclic compounds might be the origin.     

Environmental correlates of large-scale spatial variation in the δ15N of marine animals

Marine Biology - Nitrogen stable isotopes can be used to estimate the trophic position of consumers in food webs. However, the nitrogen stable isotope ratios (δ15N) of primary producers at the...     

Contaminants in water: non-target UHPLC/MS analysis

Contamination of water resources is one of the major problems to be faced for environment preservation and sustainability. The monitoring of target compounds based on mass spectrometry and selected reaction monitoring mode is often insufficient to definitely assess the quality of surface water. Also potentially harmful non-target pollutants simultaneously present must be taken into account. Liquid chromatography coupled with tandem mass spectrometry is suitable to obtain complete information on water composition. Hybrid mass spectrometers such as triple quadrupole/linear ion trap, hybrid quadrupole/time-of-flight and linear ion trap/orbitrap analyzers should be used. Here, we review ultra-high performance liquid chromatography coupled with mass spectrometry methods developed for post-target and non-target screening analysis of water emerging contaminants, such as pesticides and their degradation products, pharmaceuticals and drug side-reaction products, surfactants and illicit drugs. The major points are the following: (1) the possibility of performing retrospective analysis only by high-resolution mass analyzer; (2) the compatibility of mass analyzer with ultra-high performance liquid chromatography; (3) the use of deconvolution software to detect unknowns; and (4) the limited availability of library database.     

Absorption and retention of polydimethylsiloxanes (silicones) in fish: Preliminary experiments†

Hydrophobicity and bioaccumulation potential of linear and cyclic polydimethylsiloxane (PDMS) oligomers were estimated by reversed‐phase liquid chromatography and feeding experiments with guppies (Poecilia reticulata). PDMS concentrations in fish were determined by capillary column gas chromatography and gas chromatography‐mass spectrometry. In contrast to polychlorinated biphenyls (PCBs), only very small amounts of PDMS were retained by the fish after six weeks feeding.     

Characterization of environmental water samples using strontium and lead stable isotope compositions

A simple procedure using both cation and anion exchange chromatography has been applied in the study of lead and strontium isotope composition in rain and stream water samples from remote catchments in Scotland. Whereas the soil released strontium to stream waters, lead was removed from rain water and the concentrations in stream waters were very low. Highly precise analysis by thermal ionisation mass spectrometry proved necessary in the determination of strontium isotope composition. The ⁸⁷Sr/⁸⁶Sr ratio in rain water was close to that of marine strontium but the ratios in stream waters were constant and highly characteristic for the stream. In the case of the stream at the Sourhope site, the ratio (0.70798 ± 0.00005) was less than that in rain water and probably resulted from the weathering of one specific mineral. The results suggested that the ⁸⁷Sr/⁸⁶Sr ratios could be used as a stable isotope tracer of waters and to provide information on the weathering processes. Two major anthropogenic components of lead were identified in water samples. One had its origin in petrol additives whereas the other was probably of industrial origin. The low ²⁰⁶Pb/²⁰⁷Pb ratios observed in stream waters confirmed the lead as being of anthropogenic origin and the data suggested that there was a movement, albeit very small, of lead from the soil to waters.