Source apportionment and dynamic changes of carbonaceous aerosols during the haze bloom-decay process in China based on radiocarbon and organic molecular tracers

Fine carbonaceous aerosols (CAs) is the key factor influencing the currently filthy air in megacities in China, yet few studies simultaneously focus on the origins of different CAs species using specific and powerful source tracers. Here, we present a detailed source apportionment for various CAs fractions, including organic carbon (OC), water-soluble OC (WSOC), water-insoluble OC (WIOC), elemental carbon (EC) and secondary OC (SOC) in the largest cities of North (Beijing, BJ) and South China (Guangzhou, GZ), using the measurements of radiocarbon and anhydrosugars. Results show that non-fossil fuel sources such as biomass burning and biogenic emission make a significant contribution to the total CAs in Chinese megacities: 56±4 in BJ and 46±5% in GZ, respectively. The relative contributions of primary fossil carbon from coal and liquid petroleum combustions, primary non-fossil carbon and secondary organic carbon (SOC) to total carbon are 19, 28 and 54% in BJ, and 40, 15 and 46% in GZ, respectively. Non-fossil fuel sources account for 52 in BJ and 71% in GZ of SOC, respectively. These results suggest that biomass burning has a greater influence on regional particulate air pollution in North China than in South China. We observed an unabridged haze bloom-decay process in South China, which illustrates that both primary and secondary matter from fossil sources played a key role in the blooming phase of the pollution episode, while haze phase is predominantly driven by fossil-derived secondary organic matter and nitrate.

Human–climate interactions in the central Mediterranean region during the last millennia: The laminated record of Lake Butrint (Albania)

Lake Butrint (39°47 N, 20°1 E) is a ca. 21 m deep, coastal lagoon located in SW Albania where finely-laminated sediments have been continuously deposited during the last millennia. The multi-proxy analysis (sedimentology, high-resolution elemental geochemistry and pollen) of a 12 m long sediment core, supported by seven AMS radiocarbon dates and 137Cs dating, enable a precise reconstruction of the environmental change that occurred in the central Mediterranean region during the last ∼4.5 cal kyrs BP. Sediments consist of triplets of authigenic carbonates, organic matter and clayey laminae. Fluctuations in the thickness and/or presence of these different types of seasonal laminae indicate variations in water salinity, organic productivity and runoff in the lake's catchment, as a result of the complex interplay of tectonics, anthropogenic forcing and climate variability. The progradation of the Pavllo river delta, favoured by variable human activity from the nearby ancient city of Butrint, led to the progressive isolation of this hydrological system from the Ionian Sea. The system evolved from an open bay to a restricted lagoon, which is consistent with archaeological data. An abrupt increase in mass-wasting activity between 1515 and 1450 BC, likely caused by nearby seismic activity, led to the accumulation of 24 homogenites, up to 17 cm thick. They have been deposited during the onset of finely laminated sedimentation, which indicates restricted, anoxic bottom water conditions and higher salinity. Periods of maximum water salinity, biological productivity, and carbonate precipitation coincide with warmer intervals, such as the early Roman Warm Period (RWP) (500 BC–0 AD), the Medieval Climate Anomaly (MCA) (800–1400 AD) and recent times (after 1800 AD). Conversely, lower salinity and more oxic conditions, with higher clastic input were recorded during 1400–500 BC, the Late Roman and the Early Medieval periods (0–800 AD) and during the Little Ice Age (1400–1800 AD). Hydrological fluctuations recorded in Butrint are in phase with most central and western Mediterranean records and correlate with NAO variability. In contrast, opposite hydrological patterns have been recorded in the Eastern Balkans and the Levant during the last millennium, emphasizing a complex spatial variability in the region. Phases of maximum settlement intensity in Butrint (Roman-Late Antique) coincide with warmer and/or stable climate periods (0–800 AD and MCA, respectively), indicating a long-term influence of climatic conditions on human activities. The Late Holocene sedimentary record of Lake Butrint demonstrates the complex interplay of climate variability, tectonics and human impact in the recent evolution of coastal Mediterranean regions.

Dating prograde fluid pulses during subduction by in situ U–Pb and oxygen isotope analysis

Keywords High-pressure fluids · Whiteschists · U–Pb dating · Oxygen isotopes · Ion microprobe · Metasomatism Introduction The subduction of crustal material to mantle depths and its chemical modification during burial and exhumation contribute to element recycling in the mantle and the formation of new crust through arc magmatism. Crustal rocks that Abstract The Dora-Maira whiteschists derive from metasomatically altered granites that experienced ultrahighpressure metamorphism at ~750 °C and 40 kbar during the Alpine orogeny. In order to investigate the P–T–time– fluid evolution of the whiteschists, we obtained U–Pb ages from zircon and monazite and combined those with trace element composition and oxygen isotopes of the accessory minerals and coexisting garnet. Zircon cores are the only remnants of the granitic protolith and still preserve a Permian age, magmatic trace element compositions and δ18O of ~10 ‰. Thermodynamic modelling of Si-rich and Si-poor whiteschist compositions shows that there are two main fluid pulses during prograde subduction between 20 and 40 kbar. In Si-poor samples, the breakdown of chlorite to garnet + fluid occurs at ~22 kbar. A first zircon rim directly overgrowing the cores has inclusions of prograde phlogopite and HREE-enriched patterns indicating zircon growth at the onset of garnet formation. A second main fluid pulse is documented close to peak metamorphic conditions in both Si-rich and Si-poor whiteschist when talc + kyanite react to garnet + coesite + fluid. A second metamorphic overgrowth on zircon with HREE depletion was observed in the Si-poor whiteschists, whereas a single metamorphic overgrowth capturing phengite and talc inclusions was observed in the Si-rich whiteschists. Garnet rims, zircon rims and monazite are in chemical and isotopic equilibrium for oxygen, demonstrating that they all formed at peak metamorphism at 35 Ma as constrained by the age of monazite (34.7 ± 0.4 Ma) and zircon rims (35.1 ± 0.8 Ma). The prograde zircon rim in Si-poor whiteschists has an age that is within error indistinguishable from the age of peak metamorphic conditions, consistent with a minimum rate of subduction of 2 cm/year for the Dora-Maira unit. Oxygen isotope values for zircon rims, monazite and garnet are equal within error at 6.4 ± 0.4 ‰, which is in line with closed-system equilibrium fractionation during prograde to peak temperatures. The resulting equilibrium Δ18Ozircon-monazite at 700 ± 20 °C is 0.1 ± 0.7 ‰. The in situ oxygen isotope data argue against an externally derived input of fluids into the whiteschists. Instead, fluidassisted zircon and monazite recrystallisation can be linked to internal dehydration reactions during prograde subduction. We propose that the major metasomatic event affecting the granite protolith was related to hydrothermal seafloor alteration post-dating Jurassic rifting, well before the onset of Alpine subduction.

Constraints on the thermal evolution of the Adriatic margin during Jurassic continental break-up: U–Pb dating of rutile from the Ivrea–Verbano Zone, Italy

The Ivrea–Verbano Zone (IVZ), northern Italy, exposes an attenuated section through the Permian lower crust that records high-temperature metamorphism under lower crustal conditions and a protracted history of extension and exhumation associated partly with the Jurassic opening of the Alpine Tethys ocean. This study presents SHRIMP U–Pb geochronology of rutile from seven granulite facies metapelites from the base of the IVZ, collected from locations spanning ~35 km along the strike of Paleozoic fabrics. Rutile crystallised during Permian high-temperature metamorphism and anatexis, yet all samples give Jurassic rutile U–Pb ages that record cooling through 650–550 °C. Rutile age distributions are dominated by a peak at ~160 Ma, with a subordinate peak at ~175 Ma. Both ~160 and ~175 Ma age populations show excellent agreement between samples, indicating that the two distinctive cooling stages they record were synchronous on a regional scale. The ~175 Ma population is interpreted to record cooling in the footwall of rift-related faults and shear zones, for which widespread activity in the Lower Jurassic has been documented along the western margin of the Adriatic plate. The ~160 Ma age population postdates the activity of all known rift-related structures within the Adriatic margin, but coincides with extensive gabbroic magmatism and exhumation of sub-continental mantle to the floor of the Alpine Tethys, west of the Ivrea Zone. We propose that this ~160 Ma early post-rift age population records regional cooling following episodic heating of the distal Adriatic margin, likely related to extreme lithospheric thinning and associated advection of the asthenosphere to shallow levels. The partial preservation of the ~175 Ma age cluster suggests that the post-rift (~160 Ma) heating pulse was of short duration. The regional consistency of the data presented here, which is in contrast to many other thermochronometers in the IVZ, demonstrates the value of the rutile U–Pb technique for probing the thermal evolution of high-grade metamorphic terrains. In the IVZ, a significant decoupling between Zr-in-rutile temperatures and U–Pb ages of rutile is observed, with the two systems recording events ~120 Ma apart.

Calibration of cosmogenic noble gas production based on ³⁶Cl-³⁶Ar ages. Part 2. The ⁸¹Kr-Kr dating technique

We calibrated the ⁸¹Kr-Kr dating system for ordinary chondrites of different sizes using independent shielding-corrected ³⁶Cl-³⁶Ar ages. Krypton concentrations and isotopic compositions were measured in bulk samples from 14 ordinary chondrites of high petrologic type and the cosmogenic Kr component was obtained by subtracting trapped Kr from phase Q. The thus-determined average cosmogenic ⁷⁸Kr/⁸³Kr, ⁸⁰Kr/⁸³Kr, ⁸²Kr/⁸³Kr, and ⁸4Kr/⁸³Kr ratiC(Lavielle and Marti 1988; Wieler 2002). The cosmogenic ⁷⁸Kr/⁸³Kr ratio is correlated with the cosmogenic 22Ne/21Ne ratio, confirming that ⁷⁸Kr/⁸³Kr is a reliable shielding indicator. Previously, ⁸¹Kr-Kr ages have been determined by assuming the cosmogenic production rate of ⁸¹Kr, P(⁸¹Kr)c, to be 0.95 times the average of the cosmogenic production rates of ⁸⁰Kr and ⁸²Kr; the factor Y = 0.95 therefore accounts for the unequal production of the various Kr isotopes (Marti 1967a). However, Y should be regarded as an empirical adjustment. For samples whose ⁸⁰Kr and ⁸²Kr concentrations may be affected by neutron-capture reactions, the shielding-dependent cosmogenic (⁷⁸Kr/⁸³Kr)c ratio has been used instead to calculate P(⁸¹Kr)/P(⁸³Kr), as for some lunar samples, this ratio has been shown to linearly increase with (⁷⁸Kr/⁸³Kr)c (Marti and Lugmair 1971). However, the ⁸¹Kr-Kr ages of our samples calculated with these methods are on average ~30% higher than their ³⁶Cl-³⁶Ar ages, indicating that most if not all the ⁸¹Kr-Kr ages determined so far are significantly too high. We therefore re-evaluated both methods to determine P(⁸¹Kr)c/P(⁸³Kr)c. Our new Y value of 0.70 ± 0.04 is more than 25% lower than the value of 0.95 used so far. Furthermore, together with literature data, our data indicate that for chondrites, P(⁸¹Kr)c/P(⁸³Kr)c is rather constant at 0.43 ± 0.02, at least for the shielding range covered by our samples ([⁷⁸Kr/⁸³Kr]c = 0.119–0.185; [22Ne/21Ne]c = 1.083–1.144), in contrast to the observations on lunar samples. As expected considering the method used, ⁸¹Kr-Kr ages calculated either directly with this new P(⁸¹Kr)c/P(⁸³Kr)c value or with our new Y value both agree with the corresponding ³⁶Cl-³⁶Ar ages. However, the average deviation of 2% indicates the accuracy of both new ⁸¹Kr-Kr dating methods and the precision of the new dating systems of ~10% is demonstrated by the low scatter in the data. Consequently, this study indicates that the ⁸¹Kr-Kr ages published so far are up to 30% too high.

Is dating violence associated with substance use and sexual risk behaviors among urban, minority, middle school youth

Background. One in 4 adolescents reports some form of dating violence each year. Dating violence among high school adolescents has been linked with several morbidity issues. However, the association between dating violence and sexual risk and/or substance use among young adolescents has rarely been studied.^ Methods. Research hypotheses were tested using a secondary data analysis from a HIV, STI, pregnancy prevention intervention study for urban middle school students.^ Results. At baseline, 21% of youth reported experiencing physical ADV victimization, 48.2% reported non-physical victimization, and 52.6% report any victimization. After adjusting for race/ethnicity, gender, and age ever having sex, alcohol use, and illicit drug use were significantly associated with several forms of ADV.^ Conclusions. Dating violence appears to be associated with early initiation of sexual behavior, as well as alcohol and drug use. Few interventions address ADV among middle school youth. Early interventions that prevent dating violence are needed. ^

The Need for School-Based Teen Dating Violence Prevention

Schools have several competing demands, and often suffer from inefficient access to needed resources. Thus, the addition of any program into an already overtaxed school system must be met with convincing evidence that 1) a need or problem exists and is relevant to the education of students, 2) the problem is amenable to change, and 3) addressing the problem is in the best interest of educators and students. The purpose of the present paper is to present a case for inclusion of teen dating violence prevention programs in middle and high schools. We also discuss a recent survey of 219 employees of a suburban school district in southeast Texas. Specifically, we examined their perceived need for and appropriateness of a school-based dating violence prevention program. The anonymous internet-based survey revealed that a majority of participants believed that teen dating violence was a problem, 19% reported having observed an instance of teen dating violence, and 82% believed school to be an appropriate outlet for the implementation of a dating violence prevention program.

Building an Evidence-Based Approach to Address Dating Violence Prevention

Purpose: To discuss the approach and recommendations related to the adoption of school based curriculum for violence prevention. Findings: Preliminary assessments suggest that middle and high school youth experience a variety of forms of violence in social and dating relationships. Such experiences have negative academic, behavioral and emotional consequences. Conclusions: The authors have clearly illuminated the need for addressing the phenomenon of dating violence. The field could benefit from more robust evidenced-based investigations that substantiate that interventions have an impact beyond attitudinal changes toward the behavior. Such academic endeavors will provide a platform to validate the inclusion of such information in a school based curriculum as act as a call for action for broad based interventions.

Foraminifer counts in core JM01-1199, and review of radiocarbon ages in the Norwegian-Barents Sea-Svalbard margin

We compare six high-resolution Holocene, sediment cores along a S-N transect on the Norwegian-Svalbard continental margin from ca 60°N to 77.4°N, northern North Atlantic. Planktonic foraminifera in the cores were investigated to show the changes in upper surface and subsurface water mass distribution and properties, including summer sea-surface temperatures (SST). The cores are located below the axis of the Norwegian Current and the West Spitsbergen Current, which today transport warm Atlantic Water to the Arctic. Sediment accumulation rates are generally high at all the core sites, allowing for a temporal resolution of 10-102 years. SST is reconstructed using different types of transfer functions, resulting in very similar SST trends, with deviations of no more than +- 1.0/1.5 °C. A transfer function based on the maximum likelihood statistical approach is found to be most relevant. The reconstruction documents an abrupt change in planktonic foraminiferal faunal composition and an associated warming at the Younger Dryas-Preboreal transition. The earliest part of the Holocene was characterized by large temperature variability, including the Preboreal Oscillations and the 8.2 k event. In general, the early Holocene was characterized by SSTs similar to those of today in the south and warmer than today in the north, and a smaller S-N temperature gradient (0.23 °C/°N) compared to the present temperature gradient (0.46 °C/°N). The southern proxy records (60-69°N) were more strongly influenced by slightly cooler subsurface water probably due to the seasonality of the orbital forcing and increased stratification due to freshening. The northern records (72-77.4°N) display a millennial-scale change associated with reduced insolation and a gradual weakening of the North Atlantic thermohaline circulation (THC). The observed northwards amplification of the early Holocene warming is comparable to the pattern of recent global warming and future climate modelling, which predicts greater warming at higher latitudes. The overall trend during mid and late Holocene was a cooling in the north, stable or weak warming in the south, and a maximum S-N SST gradient of ca 0.7 °C/°N at 5000 cal. years BP. Superimposed on this trend were several abrupt temperature shifts. Four of these shifts, dated to 9000-8000, 5500-3000 and 1000 and ~400 cal. years BP, appear to be global, as they correlate with periods of global climate change. In general, there is a good correlation between the northern North Atlantic temperature records and climate records from Norway and Svalbard.

Radiocarbon dates of sediments from ODP Site 161-976

Multiproxy paleoenvironmental records (pollen and planktonic isotope) from Ocean Drilling Program Site 976 (Alboran Sea) document rapid ocean and climate variations during the last glacial that follow the Dansgaard-Oeschger climate oscillations seen in the Greenland ice core records, thus suggesting a close link of the Mediterranean climate swings with North Atlantic climates. Continental conditions rapidly oscillated through cold-arid and warm-wet conditions in the course of stadial-interstadial climate jumps. At the time of Heinrich events, i.e., maximum meltwater flux to the North Atlantic, western Mediterranean marine microflora and microfauna show rapid cooling correlated with increasing continental dryness. Enhanced aridity conceivably points to prolonged wintertime stability of atmospheric high-pressure systems over the southwestern Mediterranean in conjunction with cooling of the North Atlantic.

Radiocarbon, isotope, biogenic, and 230Th measurements for sediment core RC10-196

The subarctic North Pacific Ocean holds a large CO2 reservoir that is currently isolated from the atmosphere by a low-salinity layer. It has recently been hypothesized that the reorganization of these high-CO2 waters may have played a crucial role in the degassing of carbon dioxide to the atmosphere during the last deglaciation. This reorganization would leave some imprint on paleo-productivity records. Here we present 230Th-normalized biogenic fluxes from an intermediate depth sediment core in the Northwest Pacific (RC10-196, 54.7°N, 177.1°E, 1007 m) and place them within the context of a synthesis of previously-published biogenic flux data from 49 deep-sea cores north of 20°N, ranging from 420 to 3968 m water depth. The 230Th-normalized opal, carbonate, and organic carbon fluxes from RC10-196 peak approximately 13,000 calendar years BP during the Bølling/Allerød (B/A) period. Our data synthesis suggests that biogenic fluxes were in general lowest during the last glacial period, increased somewhat in the Northwest Pacific during Heinrich Event 1, and reached a maximum across the entire North Pacific during the B/A period. We evaluate several mechanisms as possible drivers of deglacial change in biogenic fluxes in the North Pacific, including changes in preservation, sediment focusing, sea ice extent, iron inputs, stratification, and circulation shifts initiated in the North Atlantic and North Pacific. Our analysis suggests that while micronutrient sources likely contributed to some of the observed changes, the heterogeneity in timing of glaciogenic retreat and sea level make these mechanisms unlikely causes of region-wide contemporaneous peaks in export production. We argue that paleo-observations are most consistent with ventilation increases in both the North Pacific (during H1) and North Atlantic (during B/A) being the primary drivers of increases in biogenic flux during the deglaciation, as respectively they were likely to bring nutrients to the surface via increased vertical mixing and shoaling of the global thermocline.

High-resolution stratigraphic framework for Mediterranean sapropel S5

A high-resolution stratigraphic framework is presented for sapropel S5, which represents the low-mid latitude climate optimum of the previous interglacial period (Eemian). The framework is based on three sites along a transect from west to east through the eastern Mediterranean, and is further validated using a fourth site. This method allows expression of S5-based proxy records of Eemian climate variability along a standardised depth scale that offers unprecedented possibilities for assessment of spatial gradients and signal leads and lags in an interval where highresolution (radiocarbon-style) dating cannot be performed. Our lateral comparison of S5 sapropels suggests that the onset of S5 in ODP site 967C (Eratosthenes seamount) was 1-6 centuries delayed relative to the onsets in more westerly sites.

(Supplement Table S2) Results of 230Th/U-dating

We compared the suitability of two skeletal materials of the Atlantic brain coral Diploria strigosa for 230Th/U-dating: the commonly used bulk material comprising all skeletal elements and the denser theca wall material. Eight fossil corals of presumably Last Interglacial age from Bonaire, southern Caribbean Sea, were investigated, and several sub-samples were dated from each coral. For four corals, both the ages and the activity ratios of the bulk material and theca wall agree within uncertainty. Three corals show significantly older ages for their bulk material than for their theca wall material as well as substantially elevated 232Th content and (230Th/238U) ratios. The bulk material samples of another coral show younger ages and lower (230Th/238U) ratios than the corresponding theca wall samples. This coral also contains a considerable amount of 232Th. The application of the available open-system models developed to account for post-depositional diagenetic effects in corals shows that none of the models can successfully be applied to the Bonaire corals. The most likely explanation for this observation is that the assumptions of the models are not fulfilled by our data set. Comparison of the theca wall and bulk material data enables us to obtain information about the open-system processes that affected the corals. The corals showing apparently older ages for their bulk material were probably affected by contamination with a secondary (detrital) phase. The most likely source of the detrital material is carbonate sand. The higher (230Th/232Th) ratio of this material implies that detrital contamination would have a much stronger impact on the ages than a contaminant with a bulk Earth (230Th/232Th) ratio and that the threshold for the commonly applied 232Th reliability criterion would be much lower than the generally used value of 1 ng g^-1. The coral showing apparently younger ages for its bulk material was probably influenced by more than one diagenetic process. A potential scenario is a combination of detrital contamination and U addition by secondary pore infillings. Our results show that the dense theca wall material of D. strigosa is generally less affected by post-depositional open-system behaviour and better suited for 230Th/U-dating than the bulk material. This is also obvious from the fact that all ages of theca wall material reflect a Last Interglacial origin (~125 ka), whereas the bulk material samples are either substantially older or younger. However, for some corals, the 230Th/U-ages and activity ratios of the bulk material and the theca wall samples are similar. This shows that strictly reliable 230Th/U-ages can also be obtained from bulk material samples of exceptionally well-preserved corals. However, the bulk material samples more frequently show elevated activity ratios and ages than the corresponding theca wall samples. Our findings should be generally applicable to brain corals (Mussidae) that are found in tropical oceans worldwide and may enable reliable 230Th/U-dating of fossil corals with similar skeletal architecture, even if their bulk skeleton is altered by diagenesis. The 230Th/U-ages we consider reliable (120-130 ka), along with a recently published age of 118 ka, provide the first comprehensive dating of the elevated lower reef terrace at Bonaire (118-130 ka), which is in agreement in timing and duration with other Last Interglacial records.