Geochemical Fingerprinting by Handheld Laser‐Induced Breakdown Spectroscopy

A broad suite of geological materials was studied a using a handheld laser‐induced breakdown spectroscopy (LIBS) instrument. Because LIBS is simultaneously sensitive to all elements, the full broadband emission spectrum recorded from a single laser shot provides a ‘chemical fingerprint’ of any material – solid, liquid or gas. The distinguishing chemical characteristics of the samples analysed were identified through principal component analysis (PCA), which demonstrates how this technique for statistical analysis can be used to identify spectral differences between similar sample types based on minor and trace constituents. Partial least squares discriminant analysis (PLSDA) was used to distinguish and classify the materials, with excellent discrimination achieved for all sample types. This study illustrates through four examples (carbonate minerals and rocks, the oxide mineral pair columbite–tantalite, the silicate mineral garnet and native gold) how portable, handheld LIBS analysers can be used for real‐time chemical analysis under simulated field conditions for element or mineral identification, plus such applications as stratigraphic correlation, provenance determination and natural resource exploration.     

Sediment fingerprinting as an environmental forensics tool explaining cyanobacteria blooms in lakes

Cyanobacteria (blue-green algae) blooms in water bodies present serious public health issues with attendant economic and ecological impacts. Llyn Tegid (Lake Bala) is an important conservation and amenity asset within Snowdonia National Park, Wales which since the mid-1990s has experienced multiple toxic cyanobacteria blooms threatening the ecology and tourism-dependent local economy. Multiple working hypotheses explain the emergence of this problem, including climate change, land management linked to increased nutrient flux, hydromorphological alterations or changing trophic structure - any of which may operate individually or cumulatively to impair lake function. This paper reports the findings of a sediment fingerprinting study using dated lake cores to explore the linkages between catchment and lake management practices and the emergence of the algal blooms problem. Since 1900 AD lake bed sedimentation rates have varied from 0.06 to 1.07 g cm⁻² yr⁻¹, with a pronounced acceleration since the early 1980s. Geochemical analysis revealed increases in the concentrations of total phosphorus (TP), calcium and heavy metals such as zinc and lead consistent with eutrophication and a rising pollution burden, particularly since the late 1970s. An uncertainty-inclusive sediment fingerprinting approach was used to apportion the relative fluxes from the major catchment land cover types of improved pasture, rough grazing, forestry and channel banks. This showed improved pasture and channel banks are the dominant diffuse sources of sediment in the catchment, though forestry sources were important historically. Conversion of rough grazing to improved grassland, coupled with intensified land management and year-round livestock grazing, is concluded to provide the principal source of rising TP levels. Lake Habitat Survey and particle size analysis of lake cores demonstrate the hydromorphological impact of the River Dee Regulation Scheme, which controls water level and periodically diverts flow into Llyn Tegid from the adjacent Afon Tryweryn catchment. This hydromorphological impact has also been most pronounced since the late 1970s. It is concluded that an integrated approach combining land management to reduce agricultural runoff allied to improved water level regulation enabling recovery of littoral macrophytes offers the greatest chance halting the on-going cyanobacteria issue in Llyn Tegid.     

Multicollector ICPMS as tool for isotopic fingerprinting in environmental, biomedical and geochemical studies

Stable isotopes, such as C, N, O and S, are successfully used as classical environmental tracers. During the last few years, heavy stable isotopes are getting more and more attention as tracers and proxies in biogeochemical and environmental studies. Multicollector Inductively Coupled Plasma Mass Spectrometry （MC-ICPMS） has enabled scientists to obtain high precise isotopic analyses of heavy elements such as Cl, Ca, Fe, Cu, Zn, Hg and Pb. These isotopic systems can be used as important tracers in studying metal contaminants, biomedical processes and pollution of aquatic environments. MC-ICPMS is a powerful technique for the isotopic analysis of most elements, with the exception of light elements such as H, C, N and O and noble gases. The advantage of the ICP source is that it can ionize all elements with very high sensitivity. Various inlet systems can be used to introduce samples into the mass spectrometer, for instance gas chromatography （GC）, liquid chromatography （LC）, laser ablation, or conventional liquid nebulization. The aerosol is transported by an Ar and/or He gas flow into the ICP source where it is effectively ionized and introduced into the mass analyzer through a differential pumping system. The variable multicollector detector array allows the user to adjust the detector positions along the focal plane of the mass spectrometer so that all isotopes of interest can be measured simultaneously. Molecular interferences as carbides, nitrides, oxides, argides or doubly-charged species can show up in the mass spectrum and interfere with the elemental isotope peaks. High mass resolution is needed to effectively discriminate against these interferences. The ion optics of the Finnigan NEPTUNE is specially designed to meet this requirement and expand the power of isotope ratio measurements even to elements where previously isobaric interferences were the limit.     

Application of ~(137)Cs fingerprinting technique to interpreting sediment production records from reservoir deposits in a small catchment of the Hilly Loess Plateau, China

According to variations of 137Cs and clay contents, 44 flood couplets were identified in a profile of res- ervoir deposit with a vertical length of 28.12 m in the Yuntaishan Gully. Couplet 27 at the middle of the profile had the highest average 137Cs content of 12.65 Bq·kg?1, which indicated the 1963s' deposits, then 137Cs content decreased both downward and upward in the profile. The second top and bottom couplets had average 137Cs contents of 2.15 Bq·kg?1 and 0.92 Bq·kg?1, respectively. By integrated analysis of reservoir construction and management history, variations of 137Cs contents over the profile, sediment yields of flood couplets and rainfall data during the period of 1958-1970, individual storms related to the flood couplets were identified. 44 floods with a total sediment yield of 2.36×104 m3 occurred and flood events in a year varied between 1 and 10 times during the period of 1960-1970. 7-10 flood events occurred during the wet period of 1961-1964 with very wet autumn, while only 1-2 events during the dry period of 1965-1969. Average annual specific sediment yield was 1.29×104 t·km?2·a?1 for the Yuntaishan Gully during the period of 1960-1970, which was slightly higher than 1.11 ×104 t·km?2·a?1 for the Upper Yanhe River Basin above the Ganguyi Hydrological Station and slightly lower than 1.40 ×104 t·km?2·a?1 for the nearby Zhifang Gully during the same period. Annual specific sediment yields for the Yuntaishan Gully were correlated to the wet season's rainfalls well.     

Suspended sediment source fingerprinting in a small tropical catchment and some management implications

The targeting of sediment management strategies is a key requirement in developing countries because of the limited resources available. Such targeting is, however, hampered by the lack of reliable information on catchment sediment sources. This paper reports the results of using a quantitative composite fingerprinting technique to estimate the relative importance of the primary potential sources within the upper Kaleya catchment (63 km²) in southern Zambia. During the study period (1997–9), the load-weighted mean relative contributions to the sediment load sampled at the catchment outlet were in the order: commercial cultivation (2.0%), bush grazing (17.1%), channel banks/gullies (17.2%) and communal cultivation (63.7%). Although influenced by the timing of sediment sample collection, these results are judged to provide a meaningful assessment of sediment sources in the Kaleya catchment. They indicate that improved environmental management strategies for the study area must be comprehensive and need to reduce surface erosion and hillslope/channel connectivity in areas of bush grazing and both communal and commercial cultivation and to control gully development.     

Estimating the timescale of fluvial response to anthropogenic disturbance using two generations of dams on the South River,Massachusetts, USA

Centuries-long intensive land-use change in the north-eastern United States provides the opportunity to study the timescale of geomorphic response to anthropogenic disturbances. In this region, forest-clearing and agricultural practices following EuroAmerican settlement led to deposition of legacy sediment along valley bottoms, including behind mill dams. The South River in western Massachusetts experienced two generations of damming, beginning with mill dams up to 6-m high in the eighteenth–nineteenth century, and followed by construction of the Conway Electric Dam (CED), a 17-m-tall hydroelectric dam near the watershed outlet in 1906. We use the mercury (Hg) concentration in upstream deposits along the South River to constrain the magnitude, source, and timing of inputs to the CED impoundment. Based on cesium-137 (¹³⁷Cs) chronology and results from a sediment mixing model, remobilized legacy sediment comprised % of the sediment load in the South River prior to 1954; thereafter, from 1954 to 1980s, erosion from glacial deposits likely dominated (63 ± 14%), but with legacy sediments still a substantial source (37 ± 14%). We also use the CED reservoir deposits to estimate sediment yield through time, and find it decreased after 1952. These results are consistent with high rates of mobilization of legacy sediment as historic dams breached in the early twentieth century, and suggest rapid initial response to channel incision, followed by a long decay in the second half of the century, that is likely dependent on large flood events to access legacy sediment stored in banks. Identifying sources of sediment in a watershed and quantifying erosion rates can help to guide river restoration practices. Our findings suggest a short fluvial recovery time from the eighteenth–nineteenth century to perturbation during the first half of the twentieth century, with subsequent return to a dominant long-term signal from erosion of glacial deposits, with anthropogenic sediment persisting as a secondary source. © 2020 John Wiley & Sons, Ltd.     

用于紫菜无性系种质鉴定的计算机化DNA指纹的建立

研究用RAPD技术对条斑紫菜(Porphyra yezoensis)、坛紫菜(P.Haitanensis)、半叶紫菜(P.Katadai var.Hemiphylla)和少精紫菜(P.Oligospermatangia)的15个无性系丝状体进行了遗传多样分析,用120个Operon引物进行了筛选,从中选用来自OPJ-18和OPN-02扩增出的8条多态性条带构建了这15个紫菜无性系的DNA指纹图谱,在该图谱中每个紫菜无性系均有各自特异的DNA指纹.用1和0分别表示DNA带的出现和缺失,将各个无性系的DNA指纹用计算机语言表示,建立了15个紫菜无性系的计算机化DNA指纹;在此基础上设计了紫菜无性系种质鉴定的计算机软件PhGI.     

Population similarity analysis of indicator bacteria for source prediction of faecal pollution in a coastal lake

Biochemical fingerprinting (BF) databases of 524 enterococci and 571 Escherichia coli isolates and an antibiotic resistance analysis (ARA) database comprising of 380 E. coli isolates from four suspected sources (i.e. dogs, chickens, waterfowls, and human sewage) were developed to predict the sources of faecal pollution in a recreational coastal lake. Twenty water samples representing four sampling episodes were collected from five sites and the enterococci and E. coli population from each site were compared with those of the databases. The degree of similarity between bacterial populations was measured as population similarity (Sp) coefficient. Using the BF-database, bacterial populations of waterfowls showed the highest similarity with the water samples followed by a sewage treatment plant (STP). Higher population similarities were found between samples from STP and water samples especially at two sites (T2 and T3) which were located near the sewerage pipes collecting wastewater from the study area. When using the ARA-database, the highest similarity was found between E. coli populations from STP and water samples at sites T2 and T4. Both faecal indicators and as well as methods predicted human faecal pollution, possibly through leakage from submerged sewerage pipes. The results indicated that the Sp-analysis of faecal indicator bacterial populations from suspected sources and water samples can be used as a simple tool to predict the source(s) of faecal pollution in surface waters.     

Development of oil hydrocarbon fingerprinting and identification techniques

Oil, refined product, and pyrogenic hydrocarbons are the most frequently discovered contaminants in the environment. To effectively determine the fate of spilled oil in the environment and to successfully identify source(s) of spilled oil and petroleum products is, therefore, extremely important in many oil-related environmental studies and liability cases. This article briefly reviews the recent development of chemical analysis methodologies which are most frequently used in oil spill characterization and identification studies and environmental forensic investigations. The fingerprinting and data interpretation techniques discussed include oil spill identification protocol, tiered analytical approach, generic features and chemical composition of oils, effects of weathering on hydrocarbon fingerprinting, recognition of distribution patterns of petroleum hydrocarbons, oil type screening and differentiation, analysis of “source-specific marker” compounds, determination of diagnostic ratios of specific oil constituents, stable isotopic analysis, application of various statistical and numerical analysis tools, and application of other analytical techniques. The issue of how biogenic and pyrogenic hydrocarbons are distinguished from petrogenic hydrocarbons is also addressed.