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Bacterial biomarkers thermally released from dissolved organic matter

Hopane biomarker products were detected using microscale sealed vessel (MSSV) pyrolysis gas chromatography-mass spectrometry (GC-MS) analysis of dissolved organic matter from natural aquatic systems colonised by bacterial populations. MSSV pyrolysis can reduce the polyhydroxylated alkyl side chain of bacteriohopanepolyols, yielding saturated hopane products which are more amenable to GC-MS detection than their functionalised precursors. This example demonstrates how the thermal conditions of MSSV pyrolysis can reduce the biologically-inherited structural functionality of naturally occurring organic matter such that additional structural fragments can be detected using GC methods. This approach complements traditional analytical pyrolysis methods by providing additional speciation information useful for establishing the structures and source inputs of recent or extant organic material. ?? 2006.

Organic Geochemistry↗

Demethylation of methylmercury in bird, fish, and earthworm

Toxicity of methylmercury (MeHg) to wildlife and humans results from its binding to cysteine residues of proteins, forming MeHg-cysteinate (MeHgCys) complexes that hinder biological functions. MeHgCys complexes can be detoxified in vivo, yet how this occurs is unknown. We report that MeHgCys complexes are transformed into selenocysteinate (Hg(Sec)4) complexes in multiple animals from two phyla (a waterbird, freshwater fish, and earthworms) sampled in different geographical areas and contaminated by different Hg sources. In addition, high energy-resolution X-ray absorption spectroscopy and chromatography-ICP mass spectrometry of the waterbird liver support the binding of Hg(Sec)4 to selenoprotein P and biomineralization of Hg(Sec)4 to chemically inert nanoparticulate mercury selenide (HgSe). The results provide a foundation for understanding mercury detoxification in higher organisms, and suggest that the identified MeHgCys to Hg(Sec)4 demethylation pathway is common in nature.

Environmental Science & Technology↗

Experimental approaches to assessing the impact of a cesium chloride radiological dispersal device

The US EPA, as a part of the Chemical, Biological, Radiological-Nuclear, and Explosives (CBRNE) Research and Technology Initiative (CRTI) project team, is currently working to assess the impacts of an urban radiological dispersion device (RDD) and to develop containment and decontamination strategies. Three efforts in this area are currently underway: development of a laboratory-scale cesium chloride deposition method to mimic a RDD; assessment of cesium (Cs) penetration depth and pathways in urban materials using two dimensional (2-D) mapping laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS); and experimental determination of distribution coefficients (kd) for Cs in water-building material systems. It is critical that, when performing laboratory-scale experiments to assess the fate of Cs from an RDD, the Cs particle deposition method mimics the RDD deposition. Once Cs particles are deposited onto urban surfaces, 2-D mapping of Cs concentrations using LA-ICP-MS is a critical tool for determining Cs transport pathways through these materials. Lastly, distribution coefficients are critical for understanding the transport of Cs in urban settings when direct measurements of its penetration depth are unavailable. An assessment of the newly developed deposition method along with preliminary results from the penetration experiments are presented in this paper.

Conference Paper↗

Targeted quantitation of 6ppd-quinone in fish tissue samples with liquid chromatography-tandem mass spectrometry

The tire additive transformation product N -(1,3-dimethylbutyl)- N’ -phenyl- p -phenylenediamine-quinone (6PPD-quinone) has recently garnered global attention due to its acute toxicity to some salmonids, such as coho salmon ( Oncorhynchus kisutch ), and its ubiquitous presence in urban stormwater systems. In the present study, we developed and compared the extraction efficiency of two sample preparation methodologies for quantification of 6PPD-quinone among two fish tissue sample types that included fillet of smallmouth bass ( Micropterus dolomieu ) and whole-body samples of O. kisutch fry subjected to in vivo exposure tests with 6PPD-quinone. The two sample preparation methods tested included an accelerated solvent extraction (ASE) approach and a sonication extraction approach. Both sample preparation methods included identical purification steps for the crude sample extracts with enhanced matrix removal cartridges. The purified sample extracts were subjected to targeted analysis of 6PPD-quinone using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The results showed that extractions made with the reported ASE method demonstrated significantly higher absolute recovery (80–96%) of the extracted internal standard, [ 13 C 6 ]-6PPD-quinone, than sonication-based extractions (74–80%) in both fish tissue sample types. The proposed ASE method shows acceptable limits of quantification (0.37–0.67 ng g −1 ), linearity (R 2 > 0.996), and repeatability (RSD ≤ 9%). This work advances research capabilities for investigations on the toxicokinetic processes of 6PPD-quinone in biological samples.

Environmental Toxicology and Chemistry↗

Identifying recruitment sources across trophic levels in a large river food web

Assemblages are connected through the movement of physical and biological resources including recruits. Identifying recruitment sources for predators and their prey could help us understand how assemblages use connectivity across multiple trophic levels and whether predator and prey recruitment is coupled. Recruitment sources of organisms across multiple trophic levels can be quantified by trace element analysis of stomach contents. We used trace element analysis of otoliths to determine recruitment contributions from tributaries of predatory largemouth bass ( Micropterus salmoides ) and bowfin ( Amia calva ) and their consumed prey collected from Pools 4, 8, and 13 of the Upper Mississippi River. We used laser ablation inductively coupled mass spectrometry to quantify strontium:calcium of the core of each otolith and classified each fish to a natal origin (i.e., tributary or potential resident). We compared patterns of natal origin across study reaches, collection years, and species and with previously published origins of independently sampled prey fish. Predator and prey assemblages across all study reaches recruited from tributaries. More prey (44%) than predators (17%) recruited from tributaries. Of fishes originating from tributaries, individuals recruited from various rivers including the large Minnesota and Wisconsin Rivers and several small tributaries. Patterns in natal origin were similar among predators and prey families and among reaches, across sampling years, and between consumed prey and independently sampled prey. Tributaries consistently contributed recruits to both prey and predator fishes, leading to a coupling of predator and prey recruitment sources across space and time. Predators directly and indirectly used tributaries for recruitment and persistence through their own and their prey's recruitment. We further highlighted the utility of using consumed prey to simultaneously study the ecology of prey and predator assemblages, thereby reducing research sampling needs.

Illinois, Iowa, Minnesota, Wisconsin↗

Sedimentary organics in Glen Torridon, Gale Crater, Mars: Results from the SAM instrument suite and supporting laboratory analyses

The Sample Analysis at Mars (SAM) suite instrument on board NASA's Curiosity rover has characterized the inorganic and organic chemical composition of seven samples from the Glen Torridon (GT) clay-bearing unit. A variety of organic molecules were detected with SAM using pyrolysis (up to ∼850°C) and wet chemistry experiments coupled with evolved gas analysis (EGA) and gas chromatography-mass spectrometry. SAM EGA and GCMS analyses revealed a greater diversity and abundance of sulfur-bearing aliphatic and aromatic organic compounds in the sediments of this Gale crater unit than earlier in the mission. We also report the detection of nitrogen-containing, oxygen-containing, and chlorine-containing molecules, as well as polycyclic aromatic hydrocarbons found in GT, although the sources of some of these organics may be related to the presence of chemical reagents in the SAM instrument background. However, sulfur-bearing organics released at high temperature (≥600°C) are likely derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources and consistent with the presence of recalcitrant organic materials in the sample. The SAM measurements of the GT clay-bearing unit expand the inventory of organic matter present in Gale crater and is also consistent with the hypothesis that clay minerals played an important role in the preservation of ancient refractory organic matter on Mars. These findings deepen our understanding of the past habitability and biological potential of Gale crater.

JGR Planets↗

Atomic weights of the elements. Review 2000 (IUPAC Technical Report)

A consistent set of internationally accepted atomic weights has long been an essential aim of the scientific community because of the relevance of these values to science and technology, as well as to trade and commerce subject to ethical, legal, and international standards. The standard atomic weights of the elements are regularly evaluated, recommended, and published in updated tables by the Commission on Atomic Weights and Isotopic Abundances (CAWIA) of the International Union of Pure and Applied Chemistry (IUPAC). These values are invariably associated with carefully evaluated uncertainties. Atomic weights were originally determined by mass ratio measurements coupled with an understanding of chemical stoichiometry, but are now based almost exclusively on knowledge of the isotopic composition (derived from isotope-abundance ratio measurements) and the atomic masses of the isotopes of the elements. Atomic weights and atomic masses are now scaled to a numerical value of exactly 12 for the mass of the carbon isotope of mass number 12. Technological advances in mass spectrometry and nuclear-reaction energies have enabled atomic masses to be determined with a relative uncertainty of better than 1 ×10−7 . Isotope abundances for an increasing number of elements can be measured to better than 1 ×10−3 . The excellent precision of such measurements led to the discovery that many elements, in different specimens, display significant variations in their isotope-abundance ratios, caused by a variety of natural and industrial physicochemical processes. While such variations increasingly place a constraint on the uncertainties with which some standard atomic weights can be stated, they provide numerous opportunities for investigating a range of important phenomena in physical, chemical, cosmological, biological, and industrial processes. This review reflects the current and increasing interest of science in the measured differences between source-specific and even sample-specific atomic weights. These relative comparisons can often be made with a smaller uncertainty than is achieved in the best calibrated “absolute ” (=SI-traceable) atomic-weight determinations. Accurate determinations of the atomic weights of certain elements also influence the values of fundamental constants such as the Avogadro, Faraday, and universal gas constants. This review is in two parts: the first summarizes the development of the science of atomic-weight determinations during the 20th century; the second summarizes the changes and variations that have been recognized in the values and uncertainties of atomic weights, on an element-by-element basis, in the latter part of the 20th century.

Pure and Applied Chemistry↗

The role of vermetid gastropods in the development of the Florida Middle Ground, northeast Gulf of Mexico

The Florida Middle Ground is a complex of north to northwest trending ridges that lie approximately 180 km northwest of Tampa Bay, Florida. The irregular ridges appear on the otherwise gently sloping West Florida shelf and exhibit between 10-15 m of relief. Modern studies interpret the ridges as remnants of a Holocene coral-reef buildup that today provide a hard substrate for growth of a variety of benthic organisms including hydrocorals, scleractinians, alcyonarians, and algae. Recent rotary coring reveals that the core of the eastern ridge of the Florida Middle Ground complex consists of unconsolidated marine calcareous muddy sand that is capped by a boundstone composed primarily of the sessile vermetid gastropod Petaloconchus sp., and overlays a weathered, fossiliferous limestone. Accelerator Mass Spectrometry radiocarbon ages (uncalibrated) on the 3.6-m thick vermetid worm rock indicate that it developed during a sea-level stillstand in the early Holocene (8,225 ±30-8,910 ± 25 yr B.P.). Our observations suggest that the Florida Middle Ground is a remnant of a series of shore parallel bars that formed in the early Holocene and were capped by a 3.6-m thick unit of vermetid gastropods. During a rapid sea-level rise that began ~8,000 yr B.P. the vermetids growth ceased and the worm rock preserved the ridges structure. Diver observations document that the edges of the ridges are currently being eroded and undermined by biological activity and current action, leading to calving of large capstone blocks.

Florida↗

A practical method for the determination of total selenium in environmental samples using isotope dilution-hydride generation-inductively coupled plasma-mass spectrometry

A safe, practical, and accurate method for the determination of selenium (Se) in range of environmental samples was developed. Small sample masses, 5–20 mg, were amended with 82 Se enriched isotope for the isotope dilution (ID), preceding a multi-step wet digestion with nitric acid (HNO 3 ) and hydrogen peroxide (H 2 O 2 ). Samples were incubated in an autoclave for 3 h at 20 psi and 126°C. Digestates were subsequently reduced with concentrated hydrochloric acid to Se(IV) the most favorable valence for hydride generation (HG). The solutions were then analyzed on an ICP-MS equipped with Flow Injection system (FIAS-400). Polyatomic, isobaric, and background interferences were removed through the use of HG and ID with an 82 Se enriched isotope spike. Recoveries for certified reference materials were determined and averaged 96% for biological tissues (NRCC DOLT3, DOLT4, DORM2, TORT2, and TORT3, and NIST 2976) and 108% for estuarine sediment (NRCC PACS2) with an average coefficient of variation for replicate measurements of ∼ 3.5%. Limit of detection was 0.13 ng Se g −1 dry weight or 0.19 ng Se L −1 . This method can be broadly applied to biological tissues, sediments, suspended particulates, and water samples with minimal modifications making this method highly useful for assessing the ecotoxicology of total Se in aquatic ecosystems.

Limnology and Oceanography: Methods↗

Comparison of in vitro estrogenic activity and estrogen concentrations insource and treated waters from 25 U.S. drinking water treatment plants

In vitro bioassays have been successfully used to screen for estrogenic activity in wastewater and surface water, however, few have been applied to treated drinking water. Here, extracts of source and treated water samples were assayed for estrogenic activity using T47D-KBluc cells and analyzed by liquid chromatography-Fourier transform mass spectrometry (LC-FTMS) for natural and synthetic estrogens (including estrone, 17β-estradiol, estriol, and ethinyl estradiol). None of the estrogenswere detected above the LC-FTMS quantification limits in treated samples and only 5 source waters had quantifiable concentrations of estrone, whereas 3 treated samples and 16 source samples displayed in vitro estrogenicity. Estrone accounted for themajority of estrogenic activity in respective samples, however the remaining samples that displayed estrogenic activity had no quantitative detections of known estrogenic compounds by chemical analyses. Source water estrogenicity (max, 0.47 ng 17β-estradiol equivalents (E2Eq) L−1) was below levels that have been linked to adverse effects in fish and other aquatic organisms. Treated water estrogenicity (max, 0.078 ng E2Eq L−1) was considerably below levels that are expected to be biologically relevant to human consumers. Overall, the advantage of using in vitro techniques in addition to analytical chemical determinations was displayed by the sensitivity of the T47D-KBluc bioassay, coupled with the ability tomeasure cumulative effects of mixtures, specifically when unknown chemicals may be present.

Science of the Total Environment↗

A Carboniferous apex for the late Paleozoic icehouse

Icehouse climate systems occur across an abbreviated portion of Earth history, constituting c. 25% of the Phanerozoic record. The Late Paleozoic Ice Age (LPIA) was the most extreme and longest lasting glaciation of the Phanerozoic and is characterized by periods of acute continental-scale glaciation, separated by periods of ice minima or ice-free conditions on the order of <10 6 years. The late Paleozoic glaciogenic record of the Paraná and Kalahari basins of southern Gondwana form one of the largest, best-preserved and well-calibrated records of this glaciation. In the Carboniferous, the eastern and southern margins of the Paraná Basin and the Kalahari Basin were characterized by subglacial conditions, with evidence for continental and upland glaciers. In the latest Carboniferous, these basins transitioned from subglacial reservoirs to ice-free or ‘ice distal‘ conditions evidenced by the widespread deposition of marine deposits juxtaposed on subglacial bedforms. High-precision U–Pb zircon chemical abrasion thermal ionization mass spectrometry geochronological constraints from volcanic ash deposits in the deglacial marine black shales of the Kalahari Basin and from fluvial and coal successions, which overlie marine deposits in the Paraná Basin, indicate subglacial evidence in these regions is constrained to the Carboniferous. The loss of ice in these regions is congruent with a late Carboniferous peak in p CO 2 and widespread marine anoxia in the late Carboniferous. The permeant retreat of glaciers in basinal settings, despite an early Permian p CO 2 nadir, highlights the influence of short-term perturbations on the longer-term CO 2 record and suggests an ice threshold had been crossed in the latest Carboniferous. A definitive driver for greenhouse gases in the LPIA, such as abundant and sustained volcanic activity or an increased biological pump driven by ocean fertilization, is unresolved for this period. Lastly, the proposed Carboniferous apex for the high-latitude LPIA record is incongruent with observations from the low-latitude tropics where an early Permian peak is proposed.

Geological Society, London, Special Publications↗

Fluid inclusions in quartz crystals from South-West Africa

Quartz crystals from calcite veins of unknown age in Precambrian metasedimentary rocks at Geiaus No. 6 and Aukam farms in South-West Africa contain both primary and secondary inclusions filled with one or a variable combination of: organic liquid, moderately saline aqueous liquid, dark-colored solid, and vapor. Analysis of these materials by microscopy and by gas chromatography and mass spectrometry shows the presence of constituents of both low and high molecular weights. The former include CH 4 , C 2 H 6 , C 3 H 8 and possibly C 4 H 10 as well as CO, CO 2 , H 2 O, N 2 and H 2 . High molecular weight components are dominantly n-alkanes and isoprenoid hydrocarbons. The n-alkanes range from at least n-C 10 to n-C 33 . Concentrations of n-alkanes larger than n-C 17 decrease regularly with increasing carbon number. An homologous series of isoprenoid hydrocarbons ranging from at least C 14 to C 20 is present in unusually high concentrations. Pristane (C 19 ) is most abundant, and C 17 isoprenoid is least abundant. The molecular composition and distribution of hydrocarbons suggest biological precursors for these components. Consideration of data provided by freezing, crushing and heating experiments suggests that the pressures at the time these in part supercritical fluids were trapped probably exceeded 30–40 atm, and the minimum trapping temperature was about 120–160°C. Both primary and secondary inclusions apparently containing only organic materials were trapped by the growth of the host quartz from aqueous solution. The data obtained neither prove nor preclude Precambrian, Paleozoic or younger sources for the organic materials.

Geochimica et Cosmochimica Acta↗

Ferromanganese crusts as archives of deep water Cd isotope compositions

The geochemistry of Cd in seawater has attracted significant attention owing to the nutrient-like properties of this element. Recent culturing studies have demonstrated that Cd is a biologically important trace metal that plays a role in the sequestration of inorganic carbon. This conclusion is supported by recent isotope data for Cd dissolved in seawater and incorporated in cultured phytoplankton. These results show that plankton features isotopically light Cd while Cd-depleted surface waters typically exhibit complimentary heavy Cd isotope compositions. Seawater samples from below 900 m depth display a uniform and intermediate isotope composition of ε 114/110 Cd = +3.3 ± 0.5. This study investigates whether ferromanganese (Fe-Mn) crusts are robust archives of deep water Cd isotope compositions. To this end, Cd isotope data were obtained for the recent growth surfaces of 15 Fe-Mn crusts from the Atlantic, Pacific, Indian, and Southern oceans and two USGS Fe-Mn reference nodules using double spike multiple collector inductively coupled plasma mass spectrometry. The Fe-Mn crusts yield a mean ε 114/110 Cd of +3.2 ± 0.4 (2 SE, n = 14). Data for all but one of the samples are identical, within the analytical uncertainty of ±1.1ε 114/110 Cd (2 SD), to the mean deep water Cd isotope value. This indicates that Fe-Mn crusts record seawater Cd isotope compositions without significant isotope fractionation. A single sample from the Southern Ocean exhibits a light Cd isotope composition of ε 114/110 Cd = 0.2 ± 1.1. The origin of this signature is unclear, but it may reflect variations in deep water Cd isotope compositions related to differences in surface water Cd utilization or long-term changes in seawater ε 114/110 Cd. The results suggest that time series analyses of Fe-Mn crusts may be utilized to study changes in marine Cd utilization.

Geochemistry, Geophysics, Geosystems↗

Occurrence of triclosan, triclocarban, and its lesser chlorinated congeners in Minnesota freshwater sediments collected near wastewater treatment plants

The antimicrobial agents triclosan (TCS), triclocarban (TCC) and their associated transformation products are of increasing concern as environmental pollutants due to their potential adverse effects on humans and wildlife, including bioaccumulation and endocrine-disrupting activity. Analysis by tandem mass spectrometry of 24 paired freshwater bed sediment samples (top 10 cm) collected by the U.S. Geological Survey near 12 wastewater treatment plants (WWTPs) in Minnesota revealed TCS and TCC concentrations of up to 85 and 822 ng/g dry weight (dw), respectively. Concentrations of TCS and TCC in bed sediments collected downstream of WWTPs were significantly greater than upstream concentrations in 58% and 42% of the sites, respectively. Dichloro- and non-chlorinated carbanilides (DCC and NCC) were detected in sediments collected at all sites at concentrations of up to 160 and 1.1 ng/g dw, respectively. Overall, antimicrobial concentrations were significantly higher in lakes than in rivers and creeks, with relative abundances decreasing from TCC > TCS > DCC > NCC. This is the first statewide report on the occurrence of TCS, TCC and TCC transformation products in freshwater sediments. Moreover, the results suggest biological or chemical TCC dechlorination products to be ubiquitous in freshwater environments of Minnesota, but whether this transformation occurs in the WWTP or bed sediment remains to be determined.

Minnesota↗

Male lake char release taurocholic acid as part of a mating pheromone

The evolutionary origins of sexual preferences for chemical signals remain poorly understood, due, in part, to scant information on the molecules involved. In the current study, we identified a male pheromone in lake char ( Salvelinus namaycush ) to evaluate the hypothesis that it exploits a non-sexual preference for juvenile odour. In anadromous char species, the odour of stream-resident juveniles guides migratory adults into spawning streams. Lake char are also attracted to juvenile odour but have lost the anadromous phenotype and spawn on nearshore reefs, where juvenile odour does not persist long enough to act as a cue for spawning site selection by adults. Previous behavioural data raised the possibility that males release a pheromone that includes components of juvenile odour. Using metabolomics, we found that the most abundant molecule released by males was also released by juveniles but not females. Tandem mass spectrometry and nuclear magnetic resonance were used to identify the molecule as taurocholic acid (TCA), which was previously implicated as a component of juvenile odour. Additional chemical analyses revealed that males release TCA at high rates via their urine during the spawning season. Finally, picomolar concentrations of TCA attracted pre-spawning and spawning females but not males. Taken together, our results indicate that male lake char release TCA as a mating pheromone and support the hypothesis that the pheromone is a partial match of juvenile odour.

Journal of Experimental Biology↗

American eels produce and release bile acids that vary across life stage

The American eel ( Anguilla rostrata ) is an imperilled fish hypothesized to use conspecific cues, in part, to coordinate long‐distance migration during their multistage life history. Here, holding water and tissue from multiple American eel life stages was collected and analysed for the presence, profile and concentration of bile acids. Distinct bile acid profiles were identified in glass, elver, yellow eel and silver eel holding waters using ultraperformance liquid chromatography high‐resolution mass spectrometry and principal component analysis. Taurochenodeoxycholic acid, taurodeoxycholic acid, cholic acid, deoxycholic acid, taurolithocholic acid and taurocholic acid were detected in whole tissue of American glass eels and elvers, and in liver, intestine and gallbladder samples of late‐stage yellow eels. Bile acids were not a major component of silver eel washings or tissue. This study is novel because little was previously known about bile acids produced and emitted into the environment by American eels. Future behavioural studies could evaluate whether any bile acids produced by American eels influence conspecific migratory behaviour.

Journal of Fish Biology↗

The influence of soil development on the depth distribution and structure of soil microbial communities.

Although it has been shown that the interaction of climate and time shape the dynamics of soil organic matter (SOM) storage and preservation in soil, the role of soil microbial communities in this dynamic remains unclear. Microbial communities are present throughout soil profiles and likely play critical roles in SOM and nutrient cycling, however the influence of other factors such as soil development (i.e., age) and the composition SOM on microbial community variation with depth has yet to be quantified. Improving our understanding of the relationship between soil development, soil depth, and microbial communities may provide insight to the critical role they play in cycling and preservation of SOM, as well as more mechanistic predictions of the response of soil communities to change, such as landscape-scale changes in available moisture or temperature regimes. Here we compare soils spanning a soil age by climate gradient (i.e., climo-chronosequence) to better understand the mechanisms which influence soil microbial community structure and the molecular composition of SOM. While we observed little depth-dependence in metrics of microbial community structure (i.e., composition, diversity, dissimilarity) across the range of soil development under a wetter climate, we found significant depth-dependent changes in community metrics under a drier climate, which became more pronounced as soils became older. This shift in bacterial and archaeal community structure and diversity is most apparent below a clay-rich argillic horizon formed in the older, drier soils. The molecular composition of SOM as measured by high resolution mass spectrometry (i.e., FTICR MS) also exhibited similar shifts in composition with soil depth and age. Our results highlight how soil moisture shapes the interaction of soil development, SOM, and microbial community composition. Differences in the moisture regime between our two study sites drives differences in biogeochemical depth gradients and subsequent variation in soil microbes and SOM. This suggests that knowledge of not just the pedogenic trajectory of soil development, but also the spatial position relative to distinct pedogenic features, are important for explaining variations in the depth-dependencies of microbial communities and associated SOM.

California↗

Instability of seawater pH in the South China Sea during the mid-late Holocene: Evidence from boron isotopic composition of corals

We used positive thermal ionization mass spectrometry (PTIMS) to generate high precision ??11B records in Porites corals of the mid-late Holocene from the South China Sea (SCS). The ??11B values of the Holocene corals vary significantly, ranging from 22.2??? to 25.5???. The paleo-pH records of the SCS, reconstructed from the ??11B data, were not stable as previously thought but show a gradual increase from the Holocene thermal optimal and a sharp decrease to modern values. The latter is likely caused by the large amount of anthropogenic CO2 emissions since the Industrial Revolution but variations of atmospheric pCO2 cannot explain the pH change of the SCS before the Industrial Revolution. We suggest that variations of monsoon intensity during the mid-late Holocene may have driven the sea surface pH increase from the mid to late Holocene. Results of this study indicate that the impact of anthropogenic atmospheric CO2 emissions may have reversed the natural pH trend in the SCS since the mid-Holocene. Such ocean pH records in the current interglacial period can help us better understand the physical and biological controls on ocean pH and possibly predict the long-term impact of climate change on future ocean acidification. ?? 2008 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗