兰州市冬季气溶胶吸光特性研究——黑碳与棕色碳的区分及特征分析

为研究兰州市冬季亚微米气溶胶的吸光特性,利用2014年1月10日至2月4日黑碳仪（AE31）和高分辨率飞行时间质谱仪（HR-ToF-AMS）观测资料,对气溶胶的吸光特性进行了分析。首先根据黑碳气溶胶（BC）和棕色碳气溶胶（BrC）的光学特性差异对二者进行区分,然后分析两者的吸光特性。结果表明：观测期间亚微米气溶胶中黑碳和有机物的平均浓度分别为3.7 μg·m^-3和29.3 μg·m^-3。随着亚微米气溶胶浓度的增加,黑碳和棕色碳吸收系数均增加,但棕色碳吸收系数增加得更快。黑碳和棕色碳在550 nm处的平均吸收系数分别为（9.9±5.9）Mm^-1和（51.0±28.1）Mm^-1。棕色碳的Angstrom指数为4.4。另外,采用正定矩阵因子解析模型（PMF）将棕色碳的来源划分为六种（碳氢类有机气溶胶（HOA）、烹饪类有机气溶胶（COA）、生物质燃烧（BBOA）、燃煤排放（CCOA）、半挥发低氧化程度有机气溶胶（SV-OOA）和低挥发高氧化程度有机气溶胶（LV-OOA））,并通过多元线性回归方法计算了各来源的吸光贡献,其中BBOA和CCOA对棕色碳吸光系数的贡献为41.5%,其次是SV-OOA（32.8%）、LV-OOA（14.2%）、HOA（7.8%）和COA（3.8%）,说明一次和二次有机气溶胶均为兰州地区棕色碳的重要来源。     

An application of artificial intelligence for investigating the effect of COVID-19 lockdown on three-dimensional temperature variation in equatorial Africa

We present interesting application of artificial intelligence for investigating effect of the COVID-19 lockdown on 3-dimensional temperature variation across Nigeria (2°–15° E, 4°–14° N), in equatorial Africa. Artificial neural networks were trained to learn time-series temperature variation patterns using radio occultation measurements of atmospheric temperature from the Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC). Data used for training, validation and testing of the neural networks covered period prior to the lockdown. There was also an investigation into the viability of solar activity indicator (represented by the sunspot number) as an input for the process. The results indicated that including the sunspot number as an input for the training did not improve the network prediction accuracy. The trained network was then used to predict values for the lockdown period. Since the network was trained using pre-lockdown dataset, predictions from the network are regarded as expected temperatures, should there have been no lockdown. By comparing with the actual COSMIC measurements during the lockdown period, effects of the lockdown on atmospheric temperatures were deduced. In overall, the mean altitudinal temperatures rose by about 1.1 °C above expected values during the lockdown. An altitudinal breakdown, at 1 km resolution, reveals that the values were typically below 0.5 °C at most of the altitudes, but exceeded 1 °C at 28 and 29 km altitudes. The temperatures were also observed to drop below expected values at altitudes of 0–2 km, and 17–20 km.     

Optical and radiative properties of aerosols over Abu Dhabi in the United Arab Emirates

The present study is on the aerosol optical and radiative properties in the short-wave radiation and its climate implications at the arid city of Abu Dhabi (24.42 ^°N, 54.61 ^°E, 4.5 m MSL), in the United Arab Emirates. The direct aerosol radiative forcings (ARF) in the short-wave region at the top (TOA) and bottom of the atmosphere (BOA) are estimated using a hybrid approach, making use of discrete ordinate radiative transfer method in conjunction with the short-wave flux and spectral aerosol optical depth (AOD) measurements, over a period of 3 years (June 2012–July 2015), at Abu Dhabi located at the south-west coast of the Arabian Gulf. The inferred microphysical properties of aerosols at the measurement site indicate strong seasonal variations from the dominance of coarse mode mineral dust aerosols during spring (March–May) and summer (June–September), to the abundance of fine/accumulation mode aerosols mainly from combustion of fossil-fuel and bio-fuel during autumn (October–November) and winter (December–February) seasons. The monthly mean diurnally averaged ARF at the BOA (TOA) varies from ?13.2 Wm^?2 (～?0.96 Wm^?2) in November to ?39.4 Wm^?2 (?11.4 Wm^?2) in August with higher magnitudes of the forcing values during spring/summer seasons and lower values during autumn/winter seasons. The atmospheric aerosol forcing varies from + 12.2 Wm^?2 (November) to 28.2 Wm^?2 (June) with higher values throughout the spring and summer seasons, suggesting the importance of mineral dust aerosols towards the solar dimming. Seasonally, highest values of the forcing efficiency at the surface are observed in spring (?85.0 ± 4.1 W m^?2 τ ^?1) followed closely by winter (?79.2 ± 7.1 W m^?2 τ ^?1) and the lowest values during autumn season (?54 ± 4.3 W m^?2 τ ^?1). The study concludes with the variations of the atmospheric heating rates induced by the forcing. Highest heating rate is observed in June (0.39 K day ^?1) and the lowest in November (0.17 K day ^?1) and the temporal variability of this parameter is linearly associated with the aerosol absorption index.     

Carbonaceous aerosol transport from the Indo-Gangetic Plain to the Himalayas: Carbon isotope evidence and light absorption characteristics

The Indo-Gangetic Plain (IGP) is a major regional and global emitter of atmospheric pollutants, which adversely affect surrounding areas such as the Himalayas. We present a comprehensive dataset on carbonaceous aerosol (CA) composition, radiocarbon (Δ¹⁴C) -based source apportionment, and light absorption of total suspended particle (TSP) samples collected over a 3-year period from high-altitude Jomsom in the central Himalayas. The 3-year mean TSP, organic carbon (OC), and elemental carbon (EC) concentrations were 92.0 ± 28.6, 9.74 ± 6.31, and 2.02 ± 1.35 μg m^?3, respectively, with the highest concentrations observed during the pre-monsoon season, followed by the post-monsoon, winter, and monsoon seasons. The Δ¹⁴C analysis revealed that the contribution of fossil fuel combustion (f_fossil) to EC was 47.9% ± 11.5%, which is consistent with observations in urban and remote regions in South Asia and attests that EC likely arrives in Jomsom from upwind IGP sources via long-range transport. In addition, the lowest f_fossil (38.7% ± 13.3%) was observed in winter, indicating large contributions in this season from local biomass burning. The mass absorption cross-section of EC (MAC_EC: 8.27 ± 1.76 m²/g) and water-soluble organic carbon (MAC_WSOC: 0.98 ± 0.45 m²/g) were slightly higher and lower than those reported in urban regions, respectively, indicating that CA undergo an aging process. Organic aerosol coating during transport and variation of biomass burning probably led to the seasonal variation in MAC of two components. Overall, WSOC contributed considerably to the light absorption (11.1% ± 4.23%) of EC. The findings suggest that to protect glaciers of the Himalayas from pollution-related melting, it is essential to mitigate emissions from the IGP.     

Climatology,trend of aerosol-cloud parameters and their correlation over the Northern Indian Ocean

Aerosols are one of the important atmospheric constituents and exert indirect impact on climate through the modification of microphysical and radiative properties of clouds that in turn perturb the precipitation pattern. Thus, the long term quantification of changes in aerosol and cloud characteristics and their interactions on both temporal as well as spatial scale will provide a crucial information for the better assessment of future climate change. In present study, 18 years (2003–2020) MODerate Resolution Imaging Spectro-radiometer (MODIS) derived aerosol-cloud dataset over the Northern Indian Ocean (NIO) were analysed to assess climatology and trend of aerosol, cloud characteristics and their correlation. We found a strong heterogeneity in spatio-temporal variation of aerosol and cloud parameters over the NIO that are more prominent for the coastal region. The climatological mean of aerosol loading is found high (AOD ≥ 0.5) over the outflow region along the Indian sub-continent and low (AOD ≤ 0.2) over the northern equatorial open ocean. The climatological mean of cloud properties shows dominance of optically thicker deep convective (CTP < 600 hPa and CTT < 260 K) clouds over the southern Bay of Bengal (BoB) and thinner shallow (CTP > 700 hPa and CTT > 273 K) over the northwestern Arabian Sea (AS). Similarly, bigger effective radii (>17 µm) observed along the equatorial open ocean whereas smaller CER (<17 µm) were found over Indian sub-continental coastline and western AS. Further, trend analysis reveals an increasing pattern in AOD (0.002 yr^?1), CER (0.051 µm yr^?1), LWP (0.033 gm^?2 yr^?1) and CF (0.002 yr^?1) while COD, CTT and CTP show negative trend in order of ?0.005 yr^?1, ?0.094 K yr^?1 and ?1.160 hPa yr^?1, respectively. We also perform similar analysis for seven sub-region of interest (R1 to R7) across the NIO and results show a decreasing pattern in AOD (?0.001 yr^?1) at R4 against maximum mean AOD (0.44 ± 0.03). However, coastal sub-regions R1 and R5 illustrate maximum increase in aerosol loading (>0.003 yr^?1) suggesting a significant impact of sub-continental outflow over the regions. The spatial correlation of cloud properties with respect to AOD shows a positive slope for CER (0.14) and CF (0.48) and a negative for COD (?0.19), LWP (?0.18), CTT (?0.37), CTP (?0.41). The present study provides in-depth information about the aerosol-cloud characteristics for a long term scale over NIO and could be useful in regional aerosol-cloud interaction induced climate forcing estimation.     

COVID-19 strict lockdown impact on urban air quality and atmospheric temperature in four megacities of India

COVID-19 pandemic has forced to lockdown entire India starting from 24th March 2020 to 14th April 2020 (first phase), extended up to 3rd May 2020 (second phase), and further extended up to 17th May 2020 (third phase) with limited relaxation in non-hotspot areas. This strict lockdown has severely curtailed human activity across India. Here, aerosol concentrations of particular matters (PM) i.e., PM₁₀, PM_2.5, carbon monoxide (CO), nitrogen dioxide (NO₂), sulphur dioxide (SO₂), ammonia (NH₃) and ozone (O₃), and associated temperature fluctuation in four megacities (Delhi, Mumbai, Kolkata, and Chennai) from different regions of India were investigated. In this pandemic period, air temperature of Delhi, Kolkata, Mumbai and Chennai has decreased about 3 °C, 2.5 °C, 2 °C and 2 °C respectively. Compared to previous years and pre-lockdown period, air pollutants level and aerosol concentration (?41.91%, ?37.13%, ?54.94% and ?46.79% respectively for Delhi, Mumbai, Kolkata and Chennai) in these four megacities has improved drastically during this lockdown period. Emission of PM_2.5 has experienced the highest decrease in these megacities, which directly shows the positive impact of restricted vehicular movement. Restricted emissions produce encouraging results in terms of urban air quality and temperature, which may encourage policymakers to consider it in terms of environmental sustainability.     

Physical properties of aerosols at Maitri,Antarctica

Measurements of the submicron aerosol size distribution made at the Indian Antarctic station, Maitri (70‡45′S, 11‡44′E) from January 10th to February 24th, 1997, are reported. Total aerosol concentrations normally range from 800 to 1200 particles cm⁻³ which are typical values for the coastal stations at Antarctica in summer. Aerosol size distributions are generally trimodal and open-ended with a peak between 75 and 133 nm and two minima at 42 and 420 nm. Size distributions remain almost similar for several hours or even days in absence of any meteorological disturbance. Total aerosol concentration increases by approximately an order of magnitude whenever a low pressure system passes over the station. Based on the evolution of aerosol size-distributions during such aerosol enhancement periods, three types of cases have been identified. The nucleation mode in all three cases has been suggested to result from the photochemical conversion of the DMS emissions transported either by the marine air or by the air from the ice-melt regions around Maitri. Subsidence of midtropospheric air during the weakening of radiative inversion is suggested as a possible source of the nucleation mode particles in the third case. Growth of the nucleation mode particles by condensation, coagulation and/or by cloud processes has been suggested to be responsible for other modes in size distributions.     

Satellite Estimates of Wide-Range Suspended Sediment Concentrations in Changjiang (Yangtze) Estuary Using MERIS Data

The Changjiang (Yangtze) estuarine and coastal waters are characterized by suspended sediments over a wide range of concentrations from 20 to 2,500 mg l⁻¹. Suspended sediment plays important roles in the estuarine and coastal system and environment. Previous algorithms for satellite estimates of suspended sediment concentration (SSC) showed a great limitation in that only low to moderate concentrations (up to 50 mg l⁻¹) could be reliably estimated. In this study, we developed a semi-empirical radiative transfer (SERT) model with physically based empirical coefficients to estimate SSC from MERIS data over turbid waters with a much wider range of SSC. The model was based on the Kubelka–Munk two-stream approximation of radiative transfer theory and calibrated using datasets from in situ measurements and outdoor controlled tank experiments. The results show that the sensitivity and saturation level of remote-sensing reflectance to SSC are dependent on wavelengths and SSC levels. Therefore, the SERT model, coupled with a multi-conditional algorithm scheme adapted to satellite retrieval of wide-range SSC, was proposed. Results suggest that this method is more effective and accurate in the estimation of SSC over turbid waters.     

Aerosol particle behavior during Dust Storm and Diwali over an urban location in north western India

In this study, the aerosol behavior during two contradictory events, i.e., dust storm (DS) and Diwali (DW) has been studied over Jaipur. The aerosol particle number concentration shows distinct features between DS and DW events. The total ANC was found minimum during DS while maximum during DW. The 24 h mean of total ANC was 9.15 × 10⁴ (±7.71 × 10⁴) and 5.38 × 10⁵ (±3.73 × 10⁵ particles/l) during DS and DW, respectively. The total ANC increases from 7.78 × 10⁴ to 5.32 × 10⁵ and 3.52 × 10⁵ to 1.70 × 10⁶ particles/l in 24 h during DS and DW, respectively. In DS, the ANC in coarse mode (2 < particle diameter < 20 μm) is significantly high while in DW, the ANC in fine mode (0.3 < particle diameter < 2 μm) exhibits higher concentration. During dust episode, a significant change in ANC (3.0 × 10³ to 1.12 × 10⁵ particles/l) was observed for the particle of size range in 2.0–20 μm with a slight increase in particles number concentration (7.48 × 10⁴ to 4.20 × 10⁵ particles/l) in 0.3–2.0 μm range is also observed. During DS, the fine and coarse mode particles increased 4.61 and 36.44 times while during DW, it increased 3.83 and 0.95 times, respectively. The relatively high particle levels during DW are attributed for two reasons: local emissions due to burning of fire crackers and meteorological conditions, i.e., low wind speeds and low mixing-layer heights lead to relatively high particle concentrations.

     

Stable isotope composition of subfossil Cerastoderma glaucum shells from the Szczecin Bay brackish deposits and its palaeogeographical implications (South Baltic Coast,Poland)

The environmental conditions of the Szczecin Bay, which existed prior to Szczecin Lagoon, have been reconstructed on the basis of the stable carbon and oxygen isotope (¹⁸O and ¹³C) analysis and radiocarbon dates obtained for subfossil shells of Cerastoderma (Cardium) glaucum. The shells in the collected core were well preserved in their life positions, representing a geochemical record of past temperature variation over the middle Holocene. Three major periods with different thermal conditions have been distinguished in the interval ~ 6000–4300 cal yr BP, when the important Littorina regional transgression took place. During the first period, 6000–5250 cal yr BP, water temperature decreased by 1.4°C, and then remained constant over the second period (5250–4750 cal yr BP). In contrast, during the third period (4750–4300 cal yr BP) both δ-values were highly variable and the mean summer temperature (March–November) increased by about 3.5°C. During first two periods, δ¹⁸O and δ¹³C were significantly correlated, indicating stability of the environmental conditions.     

Variations in sulphate aerosols concentration during winter monsoon season for two consecutive years using a general circulation model

During the field cruises of the Indian Ocean Experiment (INDOEX) extensive measurements on the atmospheric chemical and aerosol composition are undertaken to study the long-range transport of air pollution from south and southeast Asia towards the Indian Ocean during the dry monsoon season in 1998 and 1999. The present paper discusses the temporal and spatial variations in aerosols and aerosol forcing during the winter monsoon season (January-March) for INDOEX first field phase (FFP) in 1998 and INDOEX intensive field phase (IFP) in 1999. An interactive chemistry/aerosol model (LMDZ.3.3) is used to investigate the variation in the spatial distribution of tropospheric sulphate aerosols during 1998 and 1999. The model results depict major enhancement in the sulphate aerosol concentrations, radiative forcing (RF) and optical depth over the Indian subcontinent and adjoining marine areas between INDOEX-FFP and IFP. A significant increase in transport of sulphate aerosols from the continents to the Indian Ocean region has also been simulated during the winter monsoon in 1999. The mean RF over INDOEX-FFP in 1998 is found to be ?1.2 Wm^–2 while it increased to ?1.85 Wm^–2 during INDOEX-IFP in 1999. Model results reveal a mean sulphate aerosol optical depth (AOD) of 0.08 and 0.14 over Indian subcontinent during 1998 and 1999, respectively. The model results suggest that elevated AOD downwind of source regions in India can significantly affect the regional air quality and adjoining marine environments.     

Iron Distribution in Size‐Resolved Aerosols Generated by UV‐Femtosecond Laser Ablation: Influence of Cell Geometry and Implications for In Situ Isotopic Determination by LA‐MC‐ICP‐MS

The influence of ablation cell geometry (Frames single‐ and HelEx two‐volume cells) and laser wavelength (198 and 266 nm) on aerosols produced by femtosecond laser ablation (fs‐LA) were evaluated. Morphologies, iron mass distribution (IMD) and ⁵⁶Fe/⁵⁴Fe ratios of particles generated from magnetite, pyrite, haematite and siderite were studied. The following two morphologies were identified: spherules (10–200 nm) and agglomerates (5–10 nm). Similarity in IMD and ablation rate at 198 and 266 nm indicates similar ablation mechanisms. ⁵⁶Fe/⁵⁴Fe ratios increased with aerodynamic particle size as a result of kinetic fractionation during laser plasma plume expansion, cooling and aerosol condensation. The HelEx cell produces smaller particles with a larger range of ⁵⁶Fe/⁵⁴Fe ratios (1.85‰) than particles from the Frames cell (1.16‰), but the bulk aerosol matches the bulk substrate for both cells, demonstrating stoichiometric fs‐LA sampling. IMD differences are the result of faster wash out of the HelEx cell allowing less time for agglomeration of small, low‐δ ⁵⁶Fe particles with larger, high‐δ ⁵⁶Fe particles in the cell. Even with a shorter ablation time, half the total Fe ion intensity, and half the ablation volume, the HelEx cell produced Fe isotope determinations for magnetite that were as precise as the Frames cell, even when the latter included an aerosol‐homogenising mixing chamber. The HelEx cell delivered a more constant stream of small particles to the ICP, producing a more stable Fe ion signal (0.7% vs. 1.5% RSE for ⁵⁶Fe in a forty‐cycle single analysis), constant instrumental mass bias and thus a more precise measurement.     

Chromium and vanadium impurities in natural green euclase and their relation to the color

Natural specimens of green gemological euclase (chemical formula BeAlSiO₄(OH)) from Brazil were investigated by electron paramagnetic resonance (EPR) and optical absorption. In addition to iron-related EPR spectra, analyzed recently in blue and colorless euclase, chromium and vanadium-related EPR spectra were also detected in green euclase. Their role as color causing centers is discussed. The results indicate that Cr³⁺ ions substitute for Al³⁺ ions in the euclase structure. The EPR rotation patterns of Cr³⁺ with electron spin S = 3/2 were analyzed with monoclinic spin Hamiltonian leading to the parameters of g _xx , g _yy and g _zz equal to 2.018, 2.001 and 1.956 and electronic fine structure parameters of D = −8.27 GHz and E = 1.11 GHz, respectively, with high asymmetry ratio E/D = 0.13. For the vanadium-related EPR spectra the situation is different. It is concluded that vanadium is incorporated as the vanadyl radical VO²⁺ with electron spin S = 1/2 with nearly axial spin Hamiltonian parameters g_zz = 1.9447, g _xx  = 1.9740 g _yy  = 1.9669 and axial hyperfine interactions due to the nuclear spin I = 7/2 of the ⁵¹V isotope leading to A _zz  = 502 MHz, A _xx  = 150 MHz and A _yy  = 163 MHz. The green color of euclase is caused by two strong broad absorption bands centered at 17,185 and 24,345 cm⁻¹ which are attributed to the ⁴A_2g → ⁴T_2g, ⁴T_1g transitions of Cr³⁺, respectively. Vanadyl radicals may introduce some absorption bands centered in the near infrared with tail extending into the visible spectral range.     

Emission of phosphine in intertidal marshes of the Yangtze Estuary

Emission of phosphine, a gaseous form of P, is presently considered a potential pathway of the P biogeochemical cycle in aquatic sediments. This study investigated the emission fluxes of phosphine and its potential production mechanisms in the intertidal marshes of the Yangtze Estuary. It is shown that the relatively high emission fluxes of phosphine were measured in warm seasons, with the values of 3.85–24.9 ng m^?2 h^?1 and 4.21–36.5 ng m^?2 h^?1 in August and September, respectively. In contrast, lower fluxes of phosphine appeared in May (1.23–6.32 ng m^?2 h^?1) and January (0.21–0.91 ng m^?2 h^?1). Also, the fluxes of phosphine were generally higher in the freshwater marsh, compared with the brackish marsh. The spatio-temporal pattern of phosphine emissions was observed to be mainly associated with sediment structure, temperature and salinity. Meanwhile, the significant correlations of phosphine emissions with sedimentary P and alkaline phosphatase activities reflect that phosphine probably derives from the microbial transformations of PO₄ and organic P. In addition, it is estimated that approximately 1.08 × 10⁶ g of phosphine is released annually from sediments into the pelagic water of the Yangtze Estuary. Therefore, it is concluded that phosphine emissions may be an important internal source of P, making a significant contribution to the occurrence of algal blooms especially during warm seasons.     

Pollen stratigraphy,vegetation and climate history of the last 215 ka in the Azzano Decimo core (plain of Friuli,north-eastern Italy)

The pollen record of the long succession of marine and continental deposits filling the subsident north-Adriatic foredeep basin (NE Italy) documents the history of vegetation, the landscape evolution and the climate forcing during the last 215 ka at the south-eastern Alpine foreland. The chronology relies on several ¹⁴C determinations as well as on estimated ages of pollen-stratigraphical and sea-level event tie-points derived from comparison with high-resolution marine records, speleothemes and ice cores.Mixed temperate rainforests persisted throughout MIS 7a–7c, being replaced by conifer forests after the local glacioeustatic regression during early MIS 6. The Alpine piedmont facing the Adriatic foredeeep was glaciated at the culmination of the penultimate glaciation, as directly testified by in situ fluvioglacial aggradation related to the building of a large morainic amphitheatre. The pollen record allows correlation with other European records and with the IRD from N-Atlantic and off Iberia, thus the duration of the penultimate glacial culmination at the southalpine fringe is estimated less than 13 ka between 148 ± 1 and >135 ka. The site was not reached by the Last Interglacial maximum sea transgression and enregistered a typical, though incomplete, Eemian forest record, lacking Mediterranean evergreen trees. A complex sequence of stadial–interstadial episodes is reconstructed during the Early and Middle Würm: major xerophyte peaks match IRD maxima occurred during Heinrich events in deep-sea cores offshore Iberia and in the N-Atlantic and allows to frame lumps of interstadial phases, marked by Picea peaks, each one including several DO warm events. Broad-leaved thermophilous forests disappeared from the north-eastern plain of Italy at the end of the Early Würm, whereas reduced populations of Abies and Fagus probably sheltered even during the Last Glacial Maximum. A renewed fluvioglacial in situ deposition between 30.4 ± 0.4 and 21.6 ± 0.5 ka cal BP sets the time and duration of the last glacial culmination in the pedemontane morainic amphitheatre. Palynomorphs from Plio-Pleistocene marine successions were reworked by glacier erosion and deposited in the lowland during both the penultimate and the last deglaciation phases. This explains a bias affecting previous pollen records from the region.     

Phytoliths as quantitative indicators for the reconstruction of past environmental conditions in China II: palaeoenvironmental reconstruction in the Loess Plateau

Quantitative reconstruction of the climatic history of the Chinese Loess Plateau is important for understanding present and past environment and climate changes in the Northern Hemisphere. Here, we reconstructed mean annual temperature (MAT) and mean annual precipitation (MAP) trends during the last 136 ka based on the analysis of phytoliths from the Weinan loess section (34°24′N, 109°30′E) near the southern part of the Loess Plateau in northern China. The reconstructions have been carried out using a Chinese phytolith–climate calibration model based on weighted averaging partial least-squares regression. A series of cold and dry events, as indicated by the reconstructed MAT and MAP, are documented in the loess during the last glacial periods, which can be temporally correlated with the North Atlantic Heinrich events. Our MAT and MAP estimations show that the coldest and/or driest period occurred at the upper part of L2 unit (Late MIS 6), where MAT dropped to ca 4.4 °C and MAP to ca 100 mm. Two other prominent cold-dry periods occurred at lower Ll-5 (ca 77–62 ka) and L1-1 (ca 23–10.5 ka) where the MAT and MAP decreased to about 6.1–6.5 °C and 150–370 mm, respectively, ca 6.6–6.2 °C and 400–200 mm lower than today. However, the highest MAT (average 14.6 °C, max. 18.1 °C) and MAP (average 757 mm, max. 1000 mm) occurred at Sl interval (MIS 5). During the interstadial of L1-4–L1-2 (MIS 3) and during the Holocene warm-wet period, the MAT was about 1–2 °C and MAP 100–150 mm higher than today in the Weinan region. The well-dated MAT and MAP reconstructions from the Chinese Loess Plateau presented in this paper are the first quantitatively reconstructed proxy record of climatic changes at the glacial–interglacial timescale that is based on phytolith data. This study also reveals a causal link between climatic instability in the Atlantic Ocean and climate variability in the Chinese Loess Plateau.     

Molybdenum Mass Fractions and Stable Isotope Compositions of Sedimentary Carbonate and Silicate Reference Materials

A double‐spike method in combination with MC‐ICP‐MS was applied to obtain molybdenum (Mo) mass fractions and stable isotope compositions in a suite of sedimentary silicate (marine, lake, stream, estuarine, organic‐rich sediment, shales, slate, chert) and carbonate reference materials (coral, dolomite, limestones, carbonatites), and a manganese nodule reference material, poorly characterised for stable Mo isotope compositions. The Mo contents vary between 0.076 and 364 μg g^?1, with low‐Mo mass fractions (< 0.29 μg g^?1) found almost exclusively in carbonates. Intermediate Mo contents (0.73–2.70 μg g^?1) are reported for silicate sediments, with the exception of chert JCh‐1 (0.24 μg g^?1), organic‐rich shale SGR‐1b (36.6 μg g^?1) and manganese nodule NOD‐A‐1 (364 μg g^?1). The Mo isotope compositions (reported as δ⁹⁸Mo relative to NIST SRM 3134) range from ?1.77 to 1.03‰, with the intermediate precision varying between ± 0.01 and ± 0.12‰ (2s) for most materials. Low‐temperature carbonates show δ⁹⁸Mo values ranging from 0.21 to 1.03‰ whereas δ⁹⁸Mo values of ?1.77 and ?0.17‰ were obtained for carbonatites CMP‐1 and COQ‐1, respectively. Silicate materials have δ⁹⁸Mo values varying from ?1.56 to 0.73‰. The range of δ⁹⁸Mo values in reference materials may thus reflect the increasingly important relevance of Mo isotope investigations in the fields of palaeoceanography, weathering, sedimentation and provenance, as well as the magmatic realm.     

Influence of dissolution/reprecipitation reactions on metamorphic greenschist to amphibolite facies mica 40Ar/39Ar ages in the Longmen Shan (eastern Tibet)

Linking ages to metamorphic stages in rocks that have experienced low‐ to medium‐grade metamorphism can be particularly tricky due to the rarity of index minerals and the preservation of mineral or compositional relicts. The timing of metamorphism and the Mesozoic exhumation of the metasedimentary units and crystalline basement that form the internal part of the Longmen Shan (eastern Tibet, Sichuan, China), are, for these reasons, still largely unconstrained, but crucial for understanding the regional tectonic evolution of eastern Tibet. In situ core‐rim ⁴⁰Ar/³⁹Ar biotite and U–Th/Pb allanite data show that amphibolite facies conditions (~10–11 kbar, 530°C to 6–7 kbar, 580°C) were reached at 210–180 Ma and that biotite records crystallization, rather than cooling, ages. These conditions are mainly recorded in the metasedimentary cover. The ⁴⁰Ar/³⁹Ar ages obtained from matrix muscovite that partially re‐equilibrated during the post peak‐P metamorphic history comprise a mixture of ages between that of early prograde muscovite relicts and the timing of late muscovite recrystallization at c. 140–120 Ma. This event marks a previously poorly documented greenschist facies metamorphic overprint. This latest stage is also recorded in the crystalline basement, and defines the timing of the greenschist overprint (7 ± 1 kbar, 370 ± 35°C). Numerical models of Ar diffusion show that the difference between ⁴⁰Ar/³⁹Ar biotite and muscovite ages cannot be explained by a slow and protracted cooling in an open system. The model and petrological results rather suggest that biotite and muscovite experienced different Ar retention and resetting histories. The Ar record in mica of the studied low‐ to medium‐grade rocks seems to be mainly controlled by dissolution–reprecipitation processes rather than by diffusive loss, and by different microstructural positions in the sample. Together, our data show that the metasedimentary cover was thickened and cooled independently from the basement prior to c. 140 Ma (with a relatively fast cooling at 4.5 ± 0.5°C/Ma between 185 and 140 Ma). Since the Lower Cretaceous, the metasedimentary cover and the crystalline basement experienced a coherent history during which both were partially exhumed. The Mesozoic history of the Eastern border of the Tibetan plateau is therefore complex and polyphase, and the basement was actively involved at least since the Early Cretaceous, changing our perspective on the contribution of the Cenozoic geology.     

The Paleozoic evolution of Central Tianshan: Geochemical and geochronological evidence

A suite of Paleozoic granitoids in Central Tianshan was studied for both geochemistry and geochronology in an effort to constrain their origin and tectonic setting. We combined LA-ICP-MS dating of zircon, standard geochemical analyses and Hf-isotopic studies of zircon to develop our tectonic model. Based on our analysis, the granitoids formed in three distinctive stages: ~ 450–400 Ma, ~ 370–350 Ma and ca. 340 Ma. The first stage (450–400 Ma) granitoids exhibit metaluminous, magnesian, high-K to shoshonitic characteristics of I-type granitoids (arc-setting), that are enriched in LREE relative to HREE with high (La/Yb)_CN values, show negative Eu anomaly and are depleted in Nb, Ta and Ti. This phase of granitoid emplacement was most likely related to the southward subduction of the Paleo-Tianshan Ocean beneath the Tarim block and the subsequent Central Tianshan arc. In contrast, the second stage granitoids (370–350 Ma) are distinctly different and are classified as calc-alkaline or shoshonitic plutons with a weak positive Eu anomaly. Within the second stage granitoids, it appears that the earlier (~ 365 Ma) granitoids fit within the A-type field whereas the younger (~ 352 Ma) granitoids plot within the post-collisional potassic field. These granitoids formed during collisions between Central Tianshan and the Tuha terrane that occurred along the northern margin of Central Tianshan. Lastly, the ca. 340 Ma granitoids are typical of volcanic arc granitoids again that probably formed during the northward subduction of the South Tianshan Ocean beneath the Central Tianshan landmass or the subsequent southward subduction of the residual Paleo-Tianshan Ocean.The Hf isotopic data of zircons from all the studied granitoids were pooled and yielded three prominent Hf T_DM^C model age populations: ca. 2400 Ma, ca. 1400 Ma and ca. 1100 Ma. The Hf-data shows a significant input of juvenile crust in addition to crustal recycling. We interpret these three phases of juvenile crustal addition to phases of global growth of continental crust (~ 2400 Ma), the addition of juvenile crust during the breakup of the Columbia supercontinent (~ 1400 Ma) and the assembly of Rodinia (~ 1100 Ma).     

Determination of Abundances of Fifty‐Two Elements in Natural Waters by ICP‐MS with Freeze‐Drying Pre‐concentration

To precisely determine the abundances of fifty‐two elements found within natural water samples, with mass fractions down to fg g^?1 level, we have developed a method which combines freeze‐drying pre‐concentration (FDC) and isotope dilution internal standardisation (ID‐IS). By sublimation of H₂O, the sample solution was reduced to < 1/50 of the original volume. To determine element abundance with accuracy better than 10%, we found that for solutions being analysed by mass spectrometry the HNO₃ concentration should be > 0.3 mol l^?1 to avoid hydrolysis. Matrix‐affected signal suppression was not significant for the solutions with NaCl concentrations lower than 0.2 and 0.1 cg g^?1 for quadrupole ICP‐MS and sector field ICP‐MS, respectively. The recovery yields of elements after FDC were 97–105%. The detection limits for the sample solutions prepared by FDC were ≤ 10 pg g^?1, except for Na, K and Ca. Blanks prepared using FDC were at pg‐levels, except for eleven elements (Na, Mg, Al, P, Ca, Mn, Fe, Co, Ni, Cu and Zn). The abundances of fifty‐two elements in bottled drinking water were determined from five different geological sources with mass fractions ranging from the fg g^?1 to μg g^?1 level with high accuracy.