Climate change facilitated the early colonization of the Azores Archipelago during medieval times.

Humans have made such dramatic and permanent changes to Earth's landscapes that much of it is now substantially and irreversibly altered from its preanthropogenic state. Remote islands, until recently isolated from humans, offer insights into how these landscapes evolved in response to human-induced perturbations. However, little is known about when and how remote systems were colonized because archaeological data and historical records are scarce and incomplete. Here, we use a multiproxy approach to reconstruct the initial colonization and subsequent environmental impacts on the Azores Archipelago. Our reconstructions provide unambiguous evidence for widespread human disturbance of this archipelago starting between 700-60+50 and 850-60+60 Common Era (CE), ca. 700 y earlier than historical records suggest the onset of Portuguese settlement of the islands. Settlement proceeded in three phases, during which human pressure on the terrestrial and aquatic ecosystems grew steadily (i.e., through livestock introductions, logging, and fire), resulting in irreversible changes. Our climate models suggest that the initial colonization at the end of the early Middle Ages (500 to 900 CE) occurred in conjunction with anomalous northeasterly winds and warmer Northern Hemisphere temperatures. These climate conditions likely inhibited exploration from southern Europe and facilitated human settlers from the northeast Atlantic. These results are consistent with recent archaeological and genetic data suggesting that the Norse were most likely the earliest settlers on the islands.

Elucidation of double-bond positions of polyunsaturated alkenes through gas chromatography/mass spectrometry analysis of mono-dimethyl disulfide derivatives.

RATIONALE: Derivatization with dimethyl disulfide (DMDS) followed by gas chromatography/mass spectrometry (GC/MS) analysis is a well-established method for locating double-bond position on the alkyl chain of mono-unsaturated compounds such as alkenes. For alkenes containing more than one double bond, however, the conventional DMDS derivatization approach forms poly- or cyclized DMDS adducts whose mass spectra are difficult to interpret in terms of double-bond positions. In this study, we report an efficient experimental procedure to produce mono-DMDS adducts for polyunsaturated alkenes with two to six double bonds. GC/MS analyses of these mono-DMDS adducts yield highly characteristic mass fragments, allowing unambiguous assignments of double-bond positions on the alkyl chain. We also apply our new approach (i.e., preferential formation of mono-DMDS adducts during derivatization with DMDS) to determine the double-bond positions of unsaturated alkenes produced by laboratory cultured Isochrysis litoralis, a haptophyte algal species. METHODS: Alkenes from different sources were derivatized with DMDS at 25°C for 20 to 160 min. The mass spectra of mono-DMDS adducts were obtained by GC/EI-MS analysis of reaction products which contain chromatographically resolved mono-DMDS adducts. RESULTS: Mass spectra of corresponding mono-DMDS adducts contain prominent diagnostic ions that allow a conclusive elucidation of double-bond positions. In culture samples of Isochrysis litoralis, a series of novel mono- to tri-unsaturated C31 alkenes (9-C31:1 , 6,9-C31:2 , 6,22-C31:2 , 6,25-C31:2 , 9,22-C31:2 , 6,9,25-C31:3 ) were discovered for the first time. CONCLUSIONS: A highly efficient DMDS derivatization approach is developed to yield abundant mono-DMDS adducts of polyunsaturated alkyl alkenes for elucidating double-bond positions using GC/MS.

The diagnostic value of soluble TIM-3 in oral squamous cell carcinoma.

Objective: To evaluate the soluble TIM-3 (sTIM-3) expression level in oral squamous cell carcinoma (OSCC) and determine its clinical diagnostic potential. Methods: The sTIM-3 and squamous cell carcinoma antigen (SCCAg) levels of 199 OSCC patients and 107 healthy individuals were assessed using an enzyme-linked immunosorbent assay and their individual and combined efficiency rates were compared. Results: The results showed higher sTIM-3 and SCCAg levels in the OSCC patients and better diagnostic potential for a combination of these markers than for their individual assessments, as well as positive correlation of sTIM-3 levels with clinicopathological factors. Conclusion: sTIM-3 is a potential novel and readily accessible OSCC biomarker, which in combination with SCCAg expression level might better diagnose OSCC patients.

Lay abstract Oral squamous cell carcinoma (OSCC) is the most common type of oral cancer. It affects the patients' swallowing, speech, appearance, social interactions and other aspects. Soluble TIM-3 (sTIM-3) is a negative regulatory molecule. Serum levels of squamous cell carcinoma antigen are closely related to the growth of OSCC tumors. Herein, the serum levels of sTIM-3 in OSCC patients were examined. This study demonstrated that the combined assessment of sTIM-3 and squamous cell carcinoma antigen expression levels might better distinguish OSCC patients from healthy individuals.

Extended megadroughts in the southwestern United States during Pleistocene interglacials.

The potential for increased drought frequency and severity linked to anthropogenic climate change in the semi-arid regions of the southwestern United States (US) is a serious concern. Multi-year droughts during the instrumental period and decadal-length droughts of the past two millennia were shorter and climatically different from the future permanent, 'dust-bowl-like' megadrought conditions, lasting decades to a century, that are predicted as a consequence of warming. So far, it has been unclear whether or not such megadroughts occurred in the southwestern US, and, if so, with what regularity and intensity. Here we show that periods of aridity lasting centuries to millennia occurred in the southwestern US during mid-Pleistocene interglacials. Using molecular palaeotemperature proxies to reconstruct the mean annual temperature (MAT) in mid-Pleistocene lacustrine sediment from the Valles Caldera, New Mexico, we found that the driest conditions occurred during the warmest phases of interglacials, when the MAT was comparable to or higher than the modern MAT. A collapse of drought-tolerant C(4) plant communities during these warm, dry intervals indicates a significant reduction in summer precipitation, possibly in response to a poleward migration of the subtropical dry zone. Three MAT cycles ∼2 °C in amplitude occurred within Marine Isotope Stage (MIS) 11 and seem to correspond to the muted precessional cycles within this interglacial. In comparison with MIS 11, MIS 13 experienced higher precessional-cycle amplitudes, larger variations in MAT (4-6 °C) and a longer period of extended warmth, suggesting that local insolation variations were important to interglacial climatic variability in the southwestern US. Comparison of the early MIS 11 climate record with the Holocene record shows many similarities and implies that, in the absence of anthropogenic forcing, the region should be entering a cooler and wetter phase.

Glacial forcing of central Indonesian hydroclimate since 60,000 y B.P.

The Indo-Pacific warm pool houses the largest zone of deep atmospheric convection on Earth and plays a critical role in global climate variations. Despite the region's importance, changes in Indo-Pacific hydroclimate on orbital timescales remain poorly constrained. Here we present high-resolution geochemical records of surface runoff and vegetation from sediment cores from Lake Towuti, on the island of Sulawesi in central Indonesia, that continuously span the past 60,000 y. We show that wet conditions and rainforest ecosystems on Sulawesi present during marine isotope stage 3 (MIS3) and the Holocene were interrupted by severe drying between ∼33,000 and 16,000 y B.P. when Northern Hemisphere ice sheets expanded and global temperatures cooled. Our record reveals little direct influence of precessional orbital forcing on regional climate, and the similarity between MIS3 and Holocene climates observed in Lake Towuti suggests that exposure of the Sunda Shelf has a weaker influence on regional hydroclimate and terrestrial ecosystems than suggested previously. We infer that hydrological variability in this part of Indonesia varies strongly in response to high-latitude climate forcing, likely through reorganizations of the monsoons and the position of the intertropical convergence zone. These findings suggest an important role for the tropical western Pacific in amplifying glacial-interglacial climate variability.

Identification of double-bond positions in isomeric alkenones from a lacustrine haptophyte.

RATIONALE: Measurements of alkenone unsaturation ratios are widely used for paleotemperature reconstructions in ocean and lake environments. Previously, we reported the discovery of a series of tri-unsaturated alkenone positional isomers (Δ(14, 21, 28) ) from oligosaline and freshwater lakes in Greenland and Alaska. In this work we provide a detailed analysis of the structures and isotopic compositions (δ(13) C and δ(2) H) of the alkenones produced by the "Greenland haptophyte". METHODS: Alkenones were extracted from sediments of Lake BrayaSø, Greenland. Alkenone double-bond positions were determined by GC/EI-MS analysis of alkenone dimethyl disulfide and cyclobutylimine derivatives. Alkenones were purified by semi-preparative HPLC using a silver(I) thiolate stationary phase. Carbon and hydrogen isotope analysis was performed by gas chromatography/isotope ratio mass spectrometry (GC/IRMS). RESULTS: A series of novel tri-unsaturated alkenone positional isomers were identified among four alkenone homologues (i.e. C37 Me , C38 Me , C38 Et , and C39 Et ) with double-bond positions at Δ(14, 21, 28) . The hydrogen isotope compositions (δ(2) H, VSMOW) of the tri-unsaturated positional isomers from C37 Me and C38 Et were slightly depleted (~ -11 ‰) relative to the common tri-unsaturated alkenone. The carbon isotope composition (δ(13) C, VPDB) of the tri-unsaturated positional isomers from the C37 Me , C38 Me , C38 Et , and C39 Et alkenones were significantly enriched (~ +4 ‰) relative to the common alkenones (di-, tri-, and tetra-unsaturated). CONCLUSIONS: The novel tri-unsaturated alkenone positional isomers produced by the Greenland haptophyte possess Δ(14, 21, 28) double-bond positions, instead of the common Δ(7, 14, 21) double-bond positions. The hydrogen isotope values suggest the novel tri-unsaturated positional isomers could be biosynthetic precursors to the tetra-unsaturated alkenones (Δ(7, 14, 21, 28) ). However, the significantly higher carbon isotope values of the tri-unsaturated positional isomers relative to the common di-, tri- and tetra-unsaturated alkenones suggest these positional isomers may have different/additional biosynthetic precursors.

Discovery of alkenones with variable methylene-interrupted double bonds: implications for the biosynthetic pathway.

Alkenones (C37 -C40 ) are highly specific biomarkers produced by certain haptophyte algae in ocean and lacustrine environments and have been widely used for paleoclimate studies. Unusual shorter-chain alkenones (SCA; e.g., C35 and C36 ) have been found in environmental and culture samples, but the origin and structure of these compounds are much less understood. The marine alkenone producer, Emiliania huxleyi CCMP2758 strain, was reported with abundant C35:2 Me (∆12, 19 ) alkenones when cultured at 15°C (Prahl et al. 2006). Here we show, when this strain is cultured at 4°C-10°C, that CCMP2758 produces abundant C35:3 Me, C36:3 Me, and small amounts of C36:3 Et alkenones with unusual double-bond positions of ∆7, 12, 19 . We determine the double-bond positions of the C35:3 Me and C36:3 Me alkenones by GC-MS analysis of the dimethyl disulfide and cyclobutylamine derivatives, and we provide the first temperature calibrations based on the unsaturation ratios of the C35 and C36 alkenones. Previous studies have found C35:2 Me (∆14, 19 ) and C36:2 Et (∆14, 19 ) alkenones with three-methylene interruption in the Black Sea sediments, but this is the first reported instance of alkenones with a mixed three- and five-methylene interruption configuration in the double-bond positions. The discovery of these alkenones allows us to propose a novel biosynthetic scheme, termed the SCA biosynthesis pathway, that simultaneously rationalizes the formation of both the C35:3 Me (∆7, 12, 19 ) alkenone in our culture and the ∆14, 19 Black Sea type alkenones without invoking new desaturases for the unusual double-bond positions.

Abrupt Holocene climate change as an important factor for human migration in West Greenland.

West Greenland has had multiple episodes of human colonization and cultural transitions over the past 4,500 y. However, the explanations for these large-scale human migrations are varied, including climatic factors, resistance to adaptation, economic marginalization, mercantile exploration, and hostile neighborhood interactions. Evaluating the potential role of climate change is complicated by the lack of quantitative paleoclimate reconstructions near settlement areas and by the relative stability of Holocene temperature derived from ice cores atop the Greenland ice sheet. Here we present high-resolution records of temperature over the past 5,600 y based on alkenone unsaturation in sediments of two lakes in West Greenland. We find that major temperature changes in the past 4,500 y occurred abruptly (within decades), and were coeval in timing with the archaeological records of settlement and abandonment of the Saqqaq, Dorset, and Norse cultures, which suggests that abrupt temperature changes profoundly impacted human civilization in the region. Temperature variations in West Greenland display an antiphased relationship to temperature changes in Ireland over centennial to millennial timescales, resembling the interannual to multidecadal temperature seesaw associated with the North Atlantic Oscillation.

Learn from orientation prior for radiograph super-resolution: Orientation operator transformer.

BACKGROUND AND OBJECTIVE: High-resolution radiographic images play a pivotal role in the early diagnosis and treatment of skeletal muscle-related diseases. It is promising to enhance image quality by introducing single-image super-resolution (SISR) model into the radiology image field. However, the conventional image pipeline, which can learn a mixed mapping between SR and denoising from the color space and inter-pixel patterns, poses a particular challenge for radiographic images with limited pattern features. To address this issue, this paper introduces a novel approach: Orientation Operator Transformer - O2former. METHODS: We incorporate an orientation operator in the encoder to enhance sensitivity to denoising mapping and to integrate orientation prior. Furthermore, we propose a multi-scale feature fusion strategy to amalgamate features captured by different receptive fields with the directional prior, thereby providing a more effective latent representation for the decoder. Based on these innovative components, we propose a transformer-based SISR model, i.e., O2former, specifically designed for radiographic images. RESULTS: The experimental results demonstrate that our method achieves the best or second-best performance in the objective metrics compared with the competitors at ×4 upsampling factor. For qualitative, more objective details are observed to be recovered. CONCLUSIONS: In this study, we propose a novel framework called O2former for radiological image super-resolution tasks, which improves the reconstruction model's performance by introducing an orientation operator and multi-scale feature fusion strategy. Our approach is promising to further promote the radiographic image enhancement field.

Cross noise level PET denoising with continuous adversarial domain generalization.

Objective.Performing positron emission tomography (PET) denoising within the image space proves effective in reducing the variance in PET images. In recent years, deep learning has demonstrated superior denoising performance, but models trained on a specific noise level typically fail to generalize well on different noise levels, due to inherent distribution shifts between inputs. The distribution shift usually results in bias in the denoised images. Our goal is to tackle such a problem using a domain generalization technique.Approach.We propose to utilize the domain generalization technique with a novel feature space continuous discriminator (CD) for adversarial training, using the fraction of events as a continuous domain label. The core idea is to enforce the extraction of noise-level invariant features. Thus minimizing the distribution divergence of latent feature representation for different continuous noise levels, and making the model general for arbitrary noise levels. We created three sets of 10%, 13%-22% (uniformly randomly selected), or 25% fractions of events from 9718F-MK6240 tau PET studies of 60 subjects. For each set, we generated 20 noise realizations. Training, validation, and testing were implemented using 1400, 120, and 420 pairs of 3D image volumes from the same or different sets. We used 3D UNet as the baseline and implemented CD to the continuous noise level training data of 13%-22% set.Main results.The proposed CD improves the denoising performance of our model trained in a 13%-22% fraction set for testing in both 10% and 25% fraction sets, measured by bias and standard deviation using full-count images as references. In addition, our CD method can improve the SSIM and PSNR consistently for Alzheimer-related regions and the whole brain.Significance.To our knowledge, this is the first attempt to alleviate the performance degradation in cross-noise level denoising from the perspective of domain generalization. Our study is also a pioneer work of continuous domain generalization to utilize continuously changing source domains.

Group 2i Isochrysidales thrive in marine and lacustrine systems with ice cover.

Global warming is causing rapid changes to the cryosphere. Predicting the future trajectory of the cryosphere requires quantitative reconstruction of its past variations. A recently identified sea-ice-associated haptophyte, known as Group 2i Isochrysidales, has given rise to a new sea-ice proxy with its characteristic alkenone distributions. However, apart from the occurrence of Group 2i Isochrysidales in regions with sea ice, and the empirical relationship between C37:4 alkenone abundance and sea-ice concentration, little is known about the ecology of these haptophyte species. Here, we systematically mapped the spatial and temporal occurrence of known Group 2i Isochrysidales based on environmental DNA in both marine and lacustrine environments. Our results indicate Group 2i is widely distributed in icy marine and lacustrine environments in both Northern and Southern Hemisphere, but is absent in warm environments. Temporally, Group 2i is part of the sea-ice algae bloom during the cold seasons, in contrast to other Isochrysidales that bloom in open waters during warm seasons. Our results indicate that ice is a prerequisite for the occurrence of the psychrophilic Group 2i haptophytes in marine and lacustrine ecosystems and further affirms its value for past ice reconstructions.

Inverse gradients in leaf wax δD and δ13C values along grass blades of Miscanthus sinensis: implications for leaf wax reproduction and plant physiology.

Compound specific hydrogen and carbon isotopic ratios of higher plant leaf waxes have been extensively used in paleoclimate and paleoenvironmental reconstructions. However, studies so far have focused on the comparison of leaf wax isotopic differences in bulk leaf samples between different plant species. We sampled three different varieties of tall grasses (Miscanthus sinensis) in six segments from base to tip and determined hydrogen and carbon isotopic ratios of leaf waxes, as well as hydrogen and oxygen isotopic ratios of leaf water samples. We found an increasing, base-to-tip hydrogen isotopic gradient along the grass blades that can probably be attributed to active leaf wax regeneration over the growth season. Carbon isotopic ratios, on the other hand, show opposite trends to hydrogen isotopic ratios along the grass blades, which may reflect different photosynthetic efficiencies at different blade locales.

The unique liquid chromatographic properties of Group 11 transition metals for the separation of unsaturated organic compounds.

Silver(I) and copper(I) are known to form reversible complexes with π bonds, which have been exploited in LC for separating unsaturated organic compounds. Prominent examples include the use of AgNO3-impregnated silica gel in LC, and the use of copper(I) salts for selective extraction of alkenes from hydrocarbon mixtures. The Dewar-Chatt-Duncanson model is often invoked to explain the interaction between Ag(I) and Cu(I) and π bonds. However, it is unclear if such a reversible interaction is directly related to their d(10) outer electronic configurations. Particularly, Au(I) has not been reported to separate olefins with different numbers of double bonds in LC. Also, there has not been a systematic comparison of the liquid chromatographic properties of other d(10) transition metal salts (e.g., Zn(II), Cd(II)), making it difficult to fully understand the observed reversible interactions of Ag(I) and Cu(I) with π bonds. We demonstrate for the first time that silica gel impregnated with all three Group 11 transition metals with 1+ oxidation state strongly and similarly retain olefin compounds in LC, while transition metals from Groups 10 and 12 do not. We also tested a range of functionalized silica gels to improve the stability of Cu(I) and Au(I) ions on the surface of the silica.

Source-free domain adaptive segmentation with class-balanced complementary self-training.

Unsupervised domain adaptation (UDA) plays a crucial role in transferring knowledge gained from a labeled source domain to effectively apply it in an unlabeled and diverse target domain. While UDA commonly involves training on data from both domains, accessing labeled data from the source domain is frequently constrained, citing concerns related to patient data privacy or intellectual property. The source-free UDA (SFUDA) can be promising to sidestep this difficulty. However, without the source domain supervision, the SFUDA methods can easily fall into the dilemma of "winner takes all", in which the majority category can dominate the deep segmentor, and the minority categories are largely ignored. In addition, the over-confident pseudo-label noise in self-training-based UDA is a long-lasting problem. To sidestep these difficulties, we propose a novel class-balanced complementary self-training (CBCOST) framework for SFUDA segmentation. Specifically, we jointly optimize the pseudo-label-based self-training with two mutually reinforced components. The first class-wise balanced pseudo-label training (CBT) explicitly exploits the fine-grained class-wise confidence to select the class-wise balanced pseudo-labeled pixels with the adaptive within-class thresholds. Second, to alleviate the pseudo-labeled noise, we propose a complementary self-training (COST) to exclude the classes that do not belong to, with a heuristic complementary label selection scheme. We evaluated our CBCOST framework on both 2D and 3D cross-modality cardiac anatomical segmentation tasks and brain tumor segmentation tasks. Our experimental results showed that our CBCOST performs better than existing SFUDA methods and yields similar performance, compared with UDA methods with the source data.

Iberian Margin surface ocean cooling led freshening during Marine Isotope Stage 6 abrupt cooling events.

The high-resolution paleoclimate records on the Iberian Margin provide an excellent archive to study the mechanism of abrupt climate events. Previous studies on the Iberian Margin proposed that the surface cooling reconstructed by the alkenone-unsaturation index coincided with surface water freshening inferred from an elevated percentage of tetra-unsaturated alkenones, C37:4%. However, recent data indicate that marine alkenone producers, coccolithophores, do not produce more C37:4 in culture as salinity decreases. Hence, the causes for high C37:4 are still unclear. Here we provide detailed alkenone measurements to trace the producers of alkenones in combination with foraminiferal Mg/Ca and oxygen isotope ratios to trace salinity variations. The results indicate that all alkenones were produced by coccolithophores and the high C37:4% reflects decrease in SST instead of freshening. Furthermore, during the millennial climate changes, a surface freshening did not always trigger a cooling, but sometimes happened in the middle of multiple-stage cooling events and likely amplified the temperature decrease.

Comprehensive analysis of alkenones by reversed-phase HPLC-MS with unprecedented selectivity, linearity and sensitivity.

Alkenones are among the most widely used paleotemperature biomarkers. Traditionally, alkenones are analyzed using gas chromatography-flame ionization detector (GC-FID), or GC-chemical ionization-mass spectrometry (GC-CI-MS). However, these methods encounter considerable challenges for samples that exhibit matrix interference or low concentrations, with GC-FID requiring tedious sample preparations and GC-CI-MS suffering from nonlinear response and a narrow linear dynamic range. Here we demonstrate that reversed-phase high pressure liquid chromatography-mass spectrometry (HPLC-MS) methods provide excellent resolution, selectivity, linearity and sensitivity for alkenones in complex matrices. We systematically compared the advantages and limitations of three mass detectors (quadrupole, Orbitrap, and quadrupole-time of flight) and two ionization modes (electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI)) for alkenone analyses. We demonstrate that ESI performs better than APCI as response factors of various unsaturated alkenones are similar. Among the three mass analyzers tested, orbitrap MS provided the lowest limit of detection (0.4, 3.8 and 8.6 pg injected masses for Orbitrap, qTOF and single quadrupole MS, respectively) and the widest linear dynamic range (600, 20 and 30 folds for Orbitrap, qTOF and single quadrupole MS, respectively). Single quadrupole MS operated in ESI mode provides accurate quantification of proxy measurements over a wide range of injection masses, and with its modest instrument cost, represents an ideal method for routine applications. Analysis of global core-top sediment samples confirmed the efficacy of HPLC-MS methods for the detection and quantification of paleotemperature proxies based on alkenones and their superiority over GC-based methods. The analytical method demonstrated in this study should also allow highly sensitive analyses of diverse aliphatic ketones in complex matrices.

Assessing the rate and timing of leaf wax regeneration in Fraxinus americana using stable hydrogen isotope labeling.

RATIONALE: Understanding leaf wax regeneration and recycling is crucial for plant physiology and paleoclimate studies. However, our recent isotope labeling experiments on a grass species (Phleum pratense) yielded different conclusions from published data on a tree species (Populus trichocarpa), with the former showing rapid regeneration and the latter little regeneration in mature leaves. It is therefore important to determine if the discrepancies in published results were due to differing dynamics of leaf wax regeneration and/or caveats in experimental methods. METHODS: Leaves from a native New England tree species (Fraxinus americana) were collected at 1 to 3 h intervals over a 2-day experimental period, and, subsequently, the leaf wax δ(2) H isotopic ratios were measured using gas chromatography/isotope ratio mass spectrometry. RESULTS: It was necessary to irrigate the tree using water with significantly higher δ(2) H values than that used for the grass in order to obtain readily measurable isotopic responses over diurnal cycles. In addition, diurnal leaf wax regeneration in Fraxinus americana was delayed by 1-4 h relative to Phleum pratense, suggesting that the latter produced leaf waxes from more recently photosynthesized substrates. CONCLUSIONS: The isotopic inertia in Fraxinus americana was due to lower leaf wax regeneration rates than in Phleum pratense by one to two orders of magnitude. The difference in the timing of leaf wax biosynthesis might partially account for the observed leaf wax hydrogen isotopic difference between trees and grasses.

Quantifying instantaneous regeneration rates of plant leaf waxes using stable hydrogen isotope labeling.

Leaf waxes protect terrestrial plants from biotic and abiotic stresses and are important sedimentary biomarkers for terrestrial plants. Thus, understanding the production and ablation of leaf waxes is critical in plant physiology and for geochemical studies. However, there have been no accurate approaches to quantify leaf wax production at different time scales. In this study, we demonstrate a novel approach to study leaf wax regeneration by irrigating plants with a pulse of deuterium-enriched water, followed by measurements of leaf wax D/H ratios by gas chromatography/isotope-ratio mass spectrometry (GC/IRMS). We demonstrate the efficacy of this approach using the grass species Phleum pratense in a greenhouse environment. Using a binary isotope mass balance model, we are able to quantify the regeneration rates of the C(16), C(18) acids and leaf waxes (C(23)-C(31) n-alkanes; C(22)-C(30) n-acids) over a diurnal cycle. Our results show that within one day 33-47% of C(16) and C(18) acids are regenerated, and thus the recycling time for these compounds is 2-3 days. For C(22)-C(26) n-alkyl lipids, 7-21% are regenerated within one day and thus they require 5-16 days to recycle. In comparison, the recycling time for long-chain n-alkyl lipids (C(27)-C(31)) is as long as 71-128 days. Our approach can be applied to different plants at shorter or longer time scales by adjusting the degree of isotopic labeling, sampling intervals and the amount of irrigation water.

The first high resolution PAH record of industrialization over the past 200 years in Liaodong Bay, northeastern China.

Polycyclic aromatic hydrocarbons (PAHs) are excellent tracers for fossil fuel combustion, natural fires and petroleum contamination, and have been widely used for reconstructing past wildfires and industrial activities at a variety of time scales. Here, for the first time, we obtain a high resolution (annual to decadal scale) record of PAHs from two parallel marine sediment cores from the Liaodong Bay, Northeastern China to reconstruct the industrial activities, spanning the past ∼ 200 years from 1815 to 2014. Our data indicate that PAH variations can be divided into four episodes: I) low (probably near background) PAHs from natural fires and domestic wood combustion during the pre-industrial period from 1815 to 1890; II) slightly increased (but with large fluctuations) PAH concentrations derived from intermittent warfare during the World War (1891-1945) and increased industrial activities after 1946 (1946-1965); III) a period of stagnation and, in some cases, reduction in PAHs during the "Cultural Revolution" (1966 to 1979); and IV) a rapid and persistent rise in PAHs post 1979 linked to fast economic development, with PAH concentrations doubled from 1979 to 2014. Changes in PAH distributions demonstrate major shifts in the dominant types of fuels over time from vegetation/wood, to coal and wood, followed by coal and petroleum (including vehicle emissions) over the past 200 years. We find that PAH records also show similar trend to domestic economy and the estimated regional Anthropocene CO2 emissions from industrial activities, suggesting sedimentary PAH fluxes could be used as an indirect and qualitative proxy to track the trend for regional anthropogenic CO2 emissions.