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USGS2012

Arsenic-induced biochemical and genotoxic effects and distribution in tissues of Sprague-Dawley rats

Arsenic (As) is a well documented human carcinogen. However, its mechanisms of toxic action and carcinogenic potential in animals have not been conclusive. In this research, we investigated the biochemical and genotoxic effects of As and studied its distribution in selected tissues of Sprague–Dawley rats. Four groups of six male rats, each weighing approximately 60 ± 2 g, were injected intraperitoneally, once a day for 5 days with doses of 5, 10, 15, 20 mg/kg BW of arsenic trioxide. A control group was also made of 6 animals injected with distilled water. Following anaesthetization, blood was collected and enzyme analysis was performed by spectrophotometry following standard protocols. At the end of experimentation, the animals were sacrificed, and the lung, liver, brain and kidney were collected 24 h after the fifth day treatment. Chromosome and micronuclei preparation was obtained from bone marrow cells. Arsenic exposure significantly increased ( p < 0.05) the activities of plasma alanine aminotransferase–glutamate pyruvate transaminase (ALT/GPT), and aspartate aminotransferase–glutamate oxaloacetate transaminase (AST/GOT), as well as the number of structural chromosomal aberrations (SCA) and frequency of micronuclei (MN) in the bone marrow cells. In contrast, the mitotic index in these cells was significantly reduced ( p < 0.05). These findings indicate that aminotransferases are candidate biomarkers for arsenic-induced hepatotoxicity. Our results also demonstrate that As has a strong genotoxic potential, as measured by the bone marrow SCA and MN tests in Sprague–Dawley rats. Total arsenic concentrations in tissues were measured by inductively coupled plasma mass spectrometry (ICP-MS). A dynamic reaction cell (DRC) with hydrogen gas was used to eliminate the ArCl interference at mass 75, in the measurement of total As. Total As doses in tissues tended to correlate with specific exposure levels.

Microchemical Journal↗

USGS2007

The abundance and distribution of diamondoids in biodegraded oils from the San Joaquin Valley: Implications for biodegradation of diamondoids in petroleum reservoirs

The biodegradability of diamondoids was investigated using a collection of crude oil samples from the San Joaquin Valley, California, that had been biodegraded to varying extent in the reservoir. Our results show that diamondoids are subjected to biodegradation, which is selective as well as stepwise. Adamantanes are generally more susceptible to biodegradation than other diamondoids, such as diamantanes and triamantanes. We report a possible pathway for the microbial degradation of adamantane. This cage hydrocarbon possibly breaks down to a metabolic intermediate through the action of microbes at higher levels of biodegradation in petroleum reservoirs. Microbial alteration has only a minor effect on diamondoid abundance in oil at low levels of biodegradation. Our results suggest that most diamondoids (with the exception of adamantane) are resistant to biodegradation, like the polycyclic terpanes (e.g. C19-C24 tricyclic terpanes, hopanes, gammacerane, oleananes, Ts, Tm, C29 Ts), steranes and diasteranes. Microbial alteration of diamondoids has a negligible impact on the quantification of oil cracking achieved using the diamondoid-biomarker method. ?? 2007 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗

USGS2014

Holocene sea surface temperature and sea ice extent in the Okhotsk and Bering Seas

Accurate prediction of future climate requires an understanding of the mechanisms of the Holocene climate; however, the driving forces, mechanisms, and processes of climate change in the Holocene associated with different time scales remain unclear. We investigated the drivers of Holocene sea surface temperature (SST) and sea ice extent in the North Pacific Ocean, and the Okhotsk and Bering Seas, as inferred from sediment core records, by using the alkenone unsaturation index as a biomarker of SST and abundances of sea ice-related diatoms ( F. cylindrus and F. oceanica ) as an indicator of sea ice extent to explore controlling mechanisms in the high-latitude Pacific. Temporal changes in alkenone content suggest that alkenone production was relatively high during the middle Holocene in the Okhotsk Sea and the western North Pacific, but highest in the late Holocene in the eastern Bering Sea and the eastern North Pacific. The Holocene variations of alkenone-SSTs at sites near Kamchatka in the Northwest Pacific, as well as in the western and eastern regions of the Bering Sea, and in the eastern North Pacific track the changes of Holocene summer insolation at 50°N, but at other sites in the western North Pacific, in the southern Okhotsk Sea, and the eastern Bering Sea they do not. In addition to insolation, other atmosphere and ocean climate drivers, such as sea ice distribution and changes in the position and activity of the Aleutian Low, may have systematically influenced the timing and magnitude of warming and cooling during the Holocene within the subarctic North Pacific. Periods of high sea ice extent in both the Okhotsk and Bering Seas may correspond to some periods of frequent or strong winter–spring dust storms in the Mongolian Gobi Desert, particularly one centered at ∼4–3 thousand years before present (kyr BP). Variation in storm activity in the Mongolian Gobi Desert region may reflect changes in the strength and positions of the Aleutian Low and Siberian High. We suggest that periods of eastward displacement or increased intensity of the Aleutian Low correspond with times of increased extent of sea ice in the western Okhotsk Sea and eastern Bering Sea.

Progress in Oceanography↗

USGS2017

Constraining the thermal history of the North American Midcontinent Rift System using carbonate clumped isotopes and organic thermal maturity indices

The Midcontinent Rift System (MRS) is a Late Mesoproterozoic (∼1.1 Ga) sequence of volcanic and sedimentary rocks exposed in the Lake Superior Region of North America. The MRS continues to be the focus of much research due to its economic mineral deposits as well as its archive of Precambrian life and tectonic processes. In order to constrain the post-depositional thermal history of the MRS, samples were analyzed for carbonate clumped isotope composition and organic thermal maturity. Clumped isotope values from sedimentary/early-diagenetic samples were partially reset during burial to temperatures between 68 and 75 °C. Solid-state reordering models indicate that maximum burial temperatures of 125–155 °C would reset the clumped isotope values to the observed temperature range prior to the onset of regional cooling and uplift. Clumped isotope results from late-stage veins in the White Pine Mine encompass a greater temperature range (49–116 °C), indicative of spatially variable hydrothermal activity and vein emplacement after burial temperatures fell below 100 °C during regional cooling and uplift. Clumped isotope and organic thermal maturity data do not indicate significant spatial differences in thermal history along the MRS. Observed variability in bulk organic matter composition and biomarker indices are therefore more likely a result of shifts in primary productivity or early-degradation processes. These results demonstrate that the MRS experienced a spatially consistent, relatively mild thermal history (125–155 °C) and is therefore a valuable archive for understanding the Late Mesoproterozoic environment.

Lake Superior↗

USGS2022

Contrasting Common Era climate and hydrology sensitivities from paired lake sediment dinosterol hydrogen isotope records in the South Pacific Convergence Zone

Hydroclimate on ‘Uvea (Wallis et Futuna) is controlled by rainfall associated with the South Pacific Convergence Zone (SPCZ), the southern hemisphere's largest precipitation feature. To extend the short observational precipitation record, the hydrogen isotopic composition of the algal lipid biomarker dinosterol (δ 2 H dinosterol ) was measured in sediment cores from two volcanic crater lakes on ‘Uvea. The modern lakes differ morphologically and chemically but both contain freshwater within the photic zone, support phytoplankton communities inclusive of dinosterol-producing dinoflagellates, and experience identical climate conditions. δ 2 H dinosterol values track lake water isotope ratios, ultimately controlled in the tropics by precipitation amount and evaporative enrichment. However, in 88-m-deep Lac Lalolalo a steadily decreasing trend in sedimentary δ 2 H dinosterol values from −227‰ around year 988 CE to modern values as low as −303‰, suggests this lake's evolution from an active volcanic setting to the present system strongly influenced δ 2 H dinosterol values. Although current hydrology and water isotope systematics may now reflect precipitation and evaporation in this lake, the interaction between these processes and large changes in basin morphology, geochemistry, and hydrology obstruct the recovery of a climate signal from Lac Lalolalo's sedimentary δ 2 H dinosterol records. This work emphasizes the importance of site replication and the use of complementary climate reconstruction tools, especially when using molecular proxies that may be sensitive to more than one environmental parameter. Contrary to its neighbor, duplicate δ 2 H dinosterol records from 23-m-deep Lac Lanutavake varied between −277‰ and −297‰ and indicate slightly drier conditions during the time-period known as the Medieval Climate Anomaly (MCA, 950–1250 CE). The δ 2 H dinosterol signal in Lac Lanutavake was muted compared to published records from ‘Upolu (Samoa) and Efate (Vanuatu) indicating that ‘Uvea's location is not as sensitive to precipitation variability at sites farther from the SPCZ central axis. Lithogenic runoff proxies combined with δ 2 H dinosterol support the interpretation of a relatively dry MCA on ‘Uvea, ‘Upolu, and Efate, potentially due to less intense precipitation, a contracted, or a more zonally oriented SPCZ.

Efate Island, Lac Lalolalo, Lac Lanoto'o, Lac Lanu↗

USGS2024

Unified 200 kyr paleohydrologic history of the Southern Great Basin: Death Valley, Searles Valley, Owens Valley and the Devils Hole cave

We present a hydroclimate synthesis of the southern Great Basin over the last two glacial-interglacial cycles focused on paleolakes in Death Valley (core DV93-1), Searles Valley (core SLAPP-SRLS17), Owens Valley (core OL92), and the Devils Hole cave. There is close agreement between the occurrence of lakes in Death Valley and the height of the water table in the Devils Hole (50 km east of Death Valley) during the last 200 kyr. Death Valley and Devils Hole have adjacent, partly overlapping, drainage areas and most likely did over the last 200 kyr. When the water table in the Devils Hole was above the threshold level of ∼5 m higher than the modern, permanent lakes existed in Death Valley. At water table elevations less than 5 m above the modern, ephemeral lakes, saline pans, and mudflats occurred in Death Valley. The close temporal agreement between inferred paleoenvironments from the sediments in the Death Valley core and the paleowater table elevation in Devils Hole suggests a common forcing and provides insight into climate variability in the southwestern United States over the last 200 kyr. Owens Valley and Searles Valley, which derived inflow waters from the Sierra Nevada via the Owens River, contain paleohydrologic records which match those from Death Valley and the Devils Hole in terms of timing and direction of water availability over the last 200 kyr, indicating a similar paleohydrologic history for the entire southern Great Basin region. Near the end of Marine Oxygen Isotope Stage 6 (MIS 6), 140 ka - 130 ka, Lake Manly in Death Valley became shallow and hypersaline, and ultimately dried up at 127.1 ka ±4.3 ka. The transition from glacial to interglacial vegetation, which involved the loss of Juniperus pollen and an increase in Quercus (oak) pollen, occurred in Death Valley core DV93-1 at 131.3 ka ±4.0 ka. Following the glacial to interglacial pollen shift, a large alkaline lake formed in Death Valley. Similar conditions (freshwater, high productivity, and a mixed, deeply oxygenated water column indicated by biomarkers) existed in Searles Lake between 135.3 +2.7 / -2.9 ka and 130.1 +2.7 / -2.6 ka, also following the juniper-oak pollen transition. Sr isotopes in calcite and sulfate minerals (gypsum, glauberite, thenardite), and the rare occurrence of the sodium carbonate mineral northupite with a low 87 Sr/ 86 Sr ratio in core DV93-1, together with organic geochemical proxies from Searles core SLAPP-SRLS17, all suggest that at this time, late MIS 6 Lake Manly in Death Valley received alkaline water via spillover from Searles Valley into Death Valley through Panamint Valley. The hydrologic connection between Searles Valley, Panamint Valley, and Death Valley at Termination II (130 ka) is documented here for this system of pluvial lakes for the first time. The Devils Hole water table decreased to +6.5 m at 140.8 ka ±3.2 ka, rose briefly to +8 m at 137.6 ka ±0.5 ka, and then dropped 8 m by 120.36 ka ±0.45 ka, when it reached an elevation similar to the modern. The pluvial lakes in Death Valley and Searles Valley may have coincided with the rise of the Devils Hole water table at ∼137.6 ka ±0.5 ka years ago, although the age models for core DV93-1 and core SLAPP-SLRS17 during the end of MIS 6 carry large uncertainties.

Quaternary Science Reviews↗

USGS2014

Correlation of gene expression and contaminat concentrations in wild largescale suckers: a field-based study

Toxic compounds such as organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ether flame retardants (PBDEs) have been detected in fish, birds, and aquatic mammals that live in the Columbia River or use food resources from within the river. We developed a custom microarray for largescale suckers (Catostomus macrocheilus) and used it to investigate the molecular effects of contaminant exposure on wild fish in the Columbia River. Using Significance Analysis of Microarrays (SAM) we identified 72 probes representing 69 unique genes with expression patterns that correlated with hepatic tissue levels of OCs, PCBs, or PBDEs. These genes were involved in many biological processes previously shown to respond to contaminant exposure, including drug and lipid metabolism, apoptosis, cellular transport, oxidative stress, and cellular chaperone function. The relation between gene expression and contaminant concentration suggests that these genes may respond to environmental contaminant exposure and are promising candidates for further field and laboratory studies to develop biomarkers for monitoring exposure of wild fish to contaminant mixtures found in the Columbia River Basin. The array developed in this study could also be a useful tool for studies involving endangered sucker species and other sucker species used in contaminant research.

Oregon;Washington↗

USGS2014

Assessing reproductive and endocrine parameters in male largescale suckers ( Catostomus macrocheilus ) along a contaminant gradient in the lower Columbia River, USA

Persistent organochlorine pollutants such as polychlorinated biphenyls (PCBs), dichlorodiphenyldichloroethylene (p,p′-DDE), and polybrominated diphenyl ethers (PBDEs) are stable, bioaccumulative, and widely found in the environment, wildlife, and the human population. To explore the hypothesis that reproduction in male fish is associated with environmental exposures in the lower Columbia River (LCR), reproductive and endocrine parameters were studied in male resident, non-anadromous largescale sucker (Catostomus macrocheilus) (LSS) in the same habitats as anadromous salmonids having conservation status. Testes, thyroid tissue and plasma collected in 2010 from Longview (LV), Columbia City (CC), and Skamania (SK; reference) were studied. Sperm morphologies and thyrocyte heights were measured by light microscopy, sperm motilities by computer-assisted sperm motion analysis, sperm adenosine triphosphate (ATP) with luciferase, and plasma vitellogenin (VTG), thyroxine (T4), and triiodothyronine (T3) by immunoassay. Sperm apoptosis, viability, mitochondrial membrane potential, nuclear DNA fragmentation, and reproductive stage were measured by flow cytometry. Sperm quality parameters (except counts) and VTG were significantly different among sites, with correlations between VTG and 7 sperm parameters. Thyrocyte heights, T4, T3, gonadosomatic index and Fulton's condition factor differed among sites, but not significantly. Sperm quality was significantly lower and VTG higher where liver contaminants and water estrogen equivalents were highest (LV site). Total PCBs (specifically PCB-138, -146, -151, -170, -174, -177, -180, -183, -187, -194, and -206) and total PBDEs (specifically BDE-47, -100, -153, and -154) were negatively correlated with sperm motility. PCB-206 and BDE-154 were positively correlated with DNA fragmentation, and pentachloroanisole and VTG were positively correlated with sperm apoptosis and negatively correlated with ATP. BDE-99 was positively correlated with sperm counts and motility; T4 was negatively correlated with counts and positively correlated with motility, thus indicating possible androgenic mechanisms and thyroid endocrine disruption. Male LSS proved to be an informative model for studying reproductive and endocrine biomarkers in the LCR.

Oregon;Washington↗

USGS2015

Endocrine disrupting alkylphenolic chemicals and other contaminants in wastewater treatment plant effluents, urban streams, and fish in the Great Lakes and Upper Mississippi River Regions

Urban streams are an integral part of the municipal water cycle and provide a point of discharge for wastewater treatment plant (WWTP) effluents, allowing additional attenuation through dilution and transformation processes, as well as a conduit for transporting contaminants to downstream water supplies. Domestic and commercial activities dispose of wastes down-the-drain, resulting in wastewater containing complex chemical mixtures that are only partially removed during treatment. A key issue associated with WWTP effluent discharge into streams is the potential to cause endocrine disruption in fish. This study provides a long-term (1999-2009) evaluation of the occurrence of alkylphenolic endocrine disrupting chemicals (EDCs) and other contaminants discharged from WWTPs into streams in the Great Lakes and Upper Mississippi River Regions (Indiana, Illinois, Michigan, Minnesota, and Ohio). The Greater Metropolitan Chicago Area Waterways, Illinois, were evaluated to determine contaminant concentrations in the major WWTP effluents and receiving streams, and assess the behavior of EDCs from their sources within the sewer collection system, through the major treatment unit processes at a WWTP, to their persistence and transport in the receiving stream. Water samples were analyzed for alkylphenolic EDCs and other contaminants, including 4-nonylphenol (NP), 4-nonylphenolpolyethoxylates (NPEO), 4-nonylphenolethoxycarboxylic acids (NPEC), 4-tert-octylphenol (OP), 4-tert-octylphenolpolyethoxylates (OPEO), bisphenol A, triclosan, ethylenediaminetetraacetic acid (EDTA), and trace elements. All of the compounds were detected in all of the WWTP effluents, with EDTA and NPEC having the greatest concentrations. The compounds also were detected in the WWTP effluent dominated rivers. Multiple fish species were collected from river and lake sites and analyzed for NP, NPEO, NPEC, OP, and OPEO. Whole-body fish tissue analysis indicated widespread occurrence of alkylphenolic compounds, with the highest concentrations occurring in streams with the greatest WWTP effluent content. Biomarkers of endocrine disruption in the fish indicated long-term exposure to estrogenic chemicals in the wastewater impacted urban waterways.

Science of the Total Environment↗

USGS2020

Relation of fish intersex to contaminants in riverine sport fishes

Endocrine active compounds (EACs) are pollutants that have been recognized as an emerging and widespread threat to aquatic ecosystems globally. Intersex, the presence of female germ cells within a predominantly male gonad, is considered a biomarker of endocrine disruption caused by EACs. We measured a suite of EACs and assessed their associated impacts on fish intersex occurrence and severity in a large, regulated river system in North Carolina and South Carolina, USA. Our specific objective was to determine the relationship of contaminants in water, sediment, and fish tissue with the occurrence and severity of the intersex condition in wild, adult black bass ( Micropterus ), sunfish ( Lepomis ), and catfish (Ictaluridae) species at 11 sites located on the Yadkin-Pee Dee River. Polycyclic aromatic hydrocarbons (PAHs), ethinylestradiol (EE2), and heavy metals were the most prevalent contaminants that exceeded effect levels for the protection of aquatic organisms. Fish intersex condition was most frequently observed and most severe in black basses and was less frequently detected and less severe in sunfishes and catfishes. The occurrence of the intersex condition in fish showed site-related effects, rather than increasing longitudinal trends from upstream to downstream. Mean black bass and catfish tissue contaminant concentrations were higher than that of sunfish, likely because of the latter's lower trophic position in the food web. Principal component analysis identified waterborne PAHs as the most correlated environmental contaminant with intersex occurrence and severity in black bass and sunfish. As indicated by the intersex condition, EACs have adverse but often variable effects on the health of wild sport fishes in this river, likely due to fluctuations in EAC inputs and the dynamic nature of the riverine system. These findings enhance the understanding of the relationship between contaminants and fish health and provide information to guide ecologically comprehensive conservation and management decisions.

North Carolina, South Carolina↗

USGS2018

Temporal evaluation of estrogenic endocrine disruption markers in smallmouth bass (Micropterus dolomieu) reveals seasonal variability in intersex

A reconnaissance project completed in 2009 identified intersex and elevated plasma vitellogenin in male smallmouth bass inhabiting the Missisquoi River, VT. In an attempt to identify the presence and seasonality of putative endocrine disrupting chemicals or other factors associated with these observations, a comprehensive reevaluation was conducted between September 2012 and June 2014. Here, we collected smallmouth bass from three physically partitioned reaches along the river to measure biomarkers of estrogenic endocrine disruption in smallmouth bass. In addition, polar organic chemical integrative samples (POCIS) were deployed to identify specific chemicals associated with biological observations. We did not observe biological differences across reaches indicating the absence of clear point source contributions to the observation of intersex. Interestingly, intersex prevalence and severity decreased in a stepwise manner over the timespan of the project. Intersex decreased from 92.8% to 28.1%. The only significant predictor of intersex prevalence was year of capture, based on logistic regression analysis. The mixed model of fish length and year-of-capture best predicted intersex severity. Intersex severity was also significantly different across late summer and early spring collections indicating seasonal changes in this metric. Plasma vitellogenin and liver vitellogenin Aa transcript abundance in males did not indicate exposure to estrogenic endocrine disrupting chemicals at any of the four sample collections. Analysis of chemicals captured by the POCIS as well as results of screening discrete water samples or POCIS extracts did not indicate the contribution of appreciable estrogenic chemicals. It is possible that unreported changes in land-use activity have ameliorated the problem, and our observations indicate recovery. Regardless, this work clearly emphasizes that single, snap shot sampling for intersex may not yield representative data given that the manifestation of this condition within a population can change dramatically over time.

Vermont↗

USGS2019

Biological and mineralogical controls over cycling of low molecular weight organic compounds along a soil chronosequence

Low molecular weight organic compounds (LMWOC) represent a small but critical component of soil organic matter (SOM) for microbial growth and metabolism. The fate of these compounds is largely under microbial control, yet outside the cell, intrinsic soil properties can also significantly influence their turnover and retention. Using a chronosequence representing 1200 ka of pedogenic development, we compared physicochemical vs biological controls on the turnover and retention of fast-cycling carbon (C), e.g. glucose (GLU) and p-hydroxybenzoic acid (PHBA). Along the chronosequence, we observed mineralogical gradients whereby amorphous constituents were greatest in intermediate-aged sites, while older sites demonstrated soils with more ordered and less reactive mineralogy. Soil microbial community composition varied along the soil chronosequence and we observed reductions in total biomass and fungal biomass from younger to older sites, but this did not affect the turnover of LMWOC. Microbial utilization of LMWOC was substrate- and soil-dependent; amorphous Fe and Al oxides reduced the respiration of PHBA but respiration from glucose remained less affected. Variation in soil mineralogy did not significantly alter recovery of PHBA within microbial biomass or fungal vs. bacterial biomarkers, suggesting that reduced respiration of the phenolic resulted from direct mineral interaction with ionizable functional groups rather than changes to microbial allocation of PHBA. We conclude patterns of soil carbon storage observed across chronosequences are moderated by mineralogical effects on microbial access to LMWOC, independent of variation in microbial community composition. Keywords: 13C; Glucose; Microbial biomass C; Organo-mineral interactions; p-Hydroxybenzoic acid; Selective dissolution mineralogical analyses

Soil Biology and Biochemistry↗

USGS2016

Longitudinal evaluation of leukocyte transcripts in killer whales ( Orcinus Orca )

Early identification of illness and/or presence of environmental and/or social stressors in free-ranging and domestic cetaceans is a priority for marine mammal health care professionals. Incorporation of leukocyte gene transcript analysis into the diagnostic tool kit has the potential to augment classical diagnostics based upon ease of sample storage and shipment, inducible nature and well-defined roles of transcription and associated downstream actions. Development of biomarkers that could serve to identify “insults” and potentially differentiate disease etiology would be of great diagnostic value. To this end, a modest number of peripheral blood leukocyte gene transcripts were selected for application to a domestic killer whale population with a focus on broad representation of inducible immunologically relevant genes. Normalized leukocyte transcript values, longitudinally acquired from 232 blood samples derived from 26 clinically healthy whales, were not visibly influenced temporally nor by sex or the specific Park in which they resided. Stability in leukocyte transcript number during periods of health enhances their potential use in diagnostics through identification of outliers. Transcript levels of two cytokine genes, IL-4 and IL-17, were highly variable within the group as compared to the other transcripts. IL-4 transcripts were typically absent. Analysis of transcript levels on the other genes of interest, on an individual animal basis, identified more outliers than were visible when analyzed in the context of the entire population. The majority of outliers (9 samples) were low, though elevated transcripts were identified for IL-17 from 2 animals and one each for Cox-2 and IL-10. The low number of outliers was not unexpected as sample selection was intentionally directed towards animals that were clinically healthy at the time of collection. Outliers may reflect animals experiencing subclinical disease that is transient and self-limiting. The immunologic knowledge derived from longitudinal immunologic studies in killer whales, as was the target of the present study, has the potential to improve diagnostics and health related decision making for this and other domestic and free-ranging cetacean species.

Veterinary Immunology and Immunopathology↗

USGS2015

Effects of the environmental estrogenic contaminants bisphenol A and 17α-ethinyl estradiol on sexual development and adult behaviors in aquatic wildlife species

Endocrine disrupting chemicals ( EDCs ), including the mass-produced component of plastics, bisphenol A (BPA) are widely prevalent in aquatic and terrestrial habitats. Many aquatic species, such as fish, amphibians, aquatic reptiles and mammals, are exposed daily to high concentrations of BPA and ethinyl estradiol (EE2), estrogen in birth control pills. In this review, we will predominantly focus on BPA and EE2, well-described estrogenic EDCs. First, the evidence that BPA and EE2 are detectable in almost all bodies of water will be discussed. We will consider how BPA affects sexual and neural development in these species, as these effects have been the best characterized across taxa. For instance, such chemicals have been in many cases reported to cause sex-reversal of males to females. Even if these chemicals do not overtly alter the gonadal sex, there are indications that several EDCs might demasculinize male-specific behaviors that are essential for attracting a mate. In so doing, these chemicals may reduce the likelihood that these males reproduce. If exposed males do reproduce, the concern is that they will then be passing on compromised genetic fitness to their offspring and transmitting potential transgenerational effects through their sperm epigenome . We will thus consider how diverse epigenetic changes might be a unifying mechanism of how BPA and EE2 disrupt several processes across species. Such changes might also serve as universal species diagnostic biomarkers of BPA and other EDCs exposure. Lastly, the evidence that estrogenic EDCs-induced effects in aquatic species might translate to humans will be considered.

General and Comparative Endocrinology↗

USGS2015

Developmental exposure to bisphenol A (BPA) alters sexual differentiation in painted turtles (Chrysemys picta)

Environmental chemicals can disrupt endocrine signaling and adversely impact sexual differentiation in wildlife. Bisphenol A (BPA) is an estrogenic chemical commonly found in a variety of habitats. In this study, we used painted turtles ( Chrysemys picta ), which have temperature-dependent sex determination (TSD), as an animal model for ontogenetic endocrine disruption by BPA. We hypothesized that BPA would override TSD and disrupt sexual development. We incubated farm-raised turtle eggs at the male-producing temperature (26 °C), randomly assigned individuals to treatment groups: control, vehicle control, 17β-estradiol (E2, 20 ng/g-egg) or 0.01, 1.0, 100 μg BPA/g-egg and harvested tissues at hatch. Typical female gonads were present in 89% of the E2-treated “males”, but in none of the control males ( n = 35). Gonads of BPA-exposed turtles had varying amounts of ovarian-like cortical (OLC) tissue and disorganized testicular tubules in the medulla. Although the percentage of males with OLCs increased with BPA dose (BPA-low = 30%, BPA-medium = 33%, BPA-high = 39%), this difference was not significant ( p = 0.85). In all three BPA treatments, SOX9 patterns revealed disorganized medullary testicular tubules and β-catenin expression in a thickened cortex. Liver vitellogenin , a female-specific liver protein commonly used as an exposure biomarker , was not induced by any of the treatments. Notably, these results suggest that developmental exposure to BPA disrupts sexual differentiation in painted turtles. Further examination is necessary to determine the underlying mechanisms of sex reversal in reptiles and how these translate to EDC exposure in wild populations.

General and Comparative Endocrinology↗

USGS2001

Evidence and characteristics of hydrolytic disproportionation of organic matter during metasomatic processes

Petroleum-geochemical analyses of carbonaceous regionally metamorphosed rocks, carbonaceous rocks from ore deposits, and alkalic plutonic rocks from diverse settings, demonstrated the presence of very low to moderately low concentrations of solvent-extractable organic matter, this observation in spite of the fact that some of these rocks were exposed to extremely high metamorphic temperatures. Biomarker and ??13C analyses established that the extractable organic matter originated as sedimentary-derived hydrocarbons. However, the chemistry of the extractable bitumen has been fundamentally transformed from that found in sediment bitumen and oils. Asphaltenes and resins, as defined in the normal petroleum-geochemical sense, are completely missing. The principal aromatic hydrocarbons present in oils and sediment bitumens (especially the methylated naphthalenes) are either in highly reduced concentrations or are missing altogether, Instead, aromatic hydrocarbons typical of sediment bitumens and oils are very minor, and a number of unidentified compounds and oxygen-bearing compounds are dominant. Relatively high concentrations of alkylated benzenes are typical. The polar "resin" fraction, eluted during column chromatography, is the principal compound group, by weight, being composed of six to eight dominant peaks present in all samples, despite the great geologic diversity of the samples. These, and other, observations suggest that a strong drive towards equilibrium exists in the "bitumen." Gas chromatograms of the saturated hydrocarbons commonly have a pronounced hump in both the n-paraffins and naphthenes, centered near the C19 to C26 carbon numbers, and a ubiquitos minimum in the n-paraffin distribution near n-C12 to n-C14. Multiple considerations dictate that the bitumen in the samples is indigenous and did not originate from either surficial field contamination or from laboratory procedures. Our observations are consistent with the hydrolytic disproportion of organic matter (HDOM), in which water and organic matter, including hydrocarbons, easily exchange hydrogen or oxygen with one another under certain conditions (Helgeson et al., 1993). The process appears to take place via well-known organic-chemical redox reaction pathways and is most evident in open-fluid systems. The conclusion that HDOM took place in the analyzed samples, thus producing the chemistry of the extractable bitumen, is supported by numerous previously published organic-geochemical studies of metamorphic, volcanic, plutonic, and ore-deposit-related rocks by other investigators. HDOM is suggested as an unrecognized geologic agent of fundamental importance. The process appears to control major chemical reactions in diverse geologic environments including, but not limited to, petroleum geology and geochemistry, regional metamorphism, and base- and precious-metal ore deposition. Copyright ?? 2001 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

USGS1997

Experiments on the role of water in petroleum formation

Pyrolysis experiments were conducted on immature petroleum source rocks under various conditions to evaluate the role of water in petroleum formation. At temperatures less than 330°C for 72 h, the thermal decomposition of kerogen to bitumen was not significantly affected by the presence or absence of liquid water in contact with heated gravel-sized source rock. However, at 330 and 350°C for 72 h, the thermal decomposition of generated bitumen was significantly affected by the presence or absence of liquid water. Carbon-carbon bond cross linking resulting in the formation of an insoluble bitumen (i.e., pyrobitumen) is the dominant reaction pathway in the absence of liquid water. Conversely, thermal cracking of carbon-carbon bonds resulting in the generation of saturate-enriched oil, which is similar to natural crude oils, is the dominant reaction pathway in the presence of liquid water. This difference in reaction pathways is explained by the availability of an exogenous source of hydrogen, which reduces the rate of thermal decomposition, promotes thermal cracking, and inhibits carbon-carbon bond cross linking. The distribution of generated n -alkanes is characteristic of a free radical mechanism, with a broad carbon-number distribution (i.e., C 5 to C 35 ) and only minor branched alkanes from known biological precursors (i.e., pristane and phytane). The generation of excess oxygen in the form of CO 2 in hydrous experiments and the high degree of hydrocarbon deuteration in a D 2 O experiment indicate that water dissolved in the bitumen is an exogenous source of hydrogen. The lack of an effect on product composition and yield with an increase in H + activity by five orders of magnitude in a hydrous experiment indicates that an ionic mechanism for water interactions with thermally decomposing bitumen is not likely. Several mechanistically simple and thermodynamically favorable reactions that are consistent with the available experimental data are envisaged for the generation of exogenous hydrogen and excess oxygen as CO 2 . One reaction series involves water oxidizing existing carbonyl groups to form hydrogen and carbonyl groups, with the latter forming CO 2 by decarbonylation with increasing thermal stress. Another reaction series involves either hydrogen or oxygen in dissolved water molecules directly interacting with unpaired electrons to form a hydrogen-terminated free-radical site or an oxygenated functional group, respectively. The latter is expected to be susceptible to oxidation by other dissolved water molecules to generate additional hydrogen and CO 2 . In addition to water acting as an exogenous source of hydrogen, it is also essential to the generation of an expelled saturate-enriched oil that is similar to natural crude oil. This role of water is demonstrated by the lack of an expelled oil in an experiment where a liquid Ga In alloy is substituted for liquid water. Experiments conducted with high salinity water and high water/rock ratios indicate that selective aqueous solubility of hydrocarbons is not responsible for the expelled oil generated in hydrous pyrolysis experiments. Similarly, a hydrous pyrolysis experiment conducted with isolated kerogen indicates that expelled oil in hydrous pyrolysis is not the result of preferential sorption of polar organic components by the mineral matrix of a source rock. It is envisaged that dissolved water in the bitumen network of a source rock causes an immiscible saturate-enriched oil to become immiscible with the thermally decomposing polar-enriched bitumen. The overall geochemical implication of these results is that it is essential to consider the role of water in experimental studies designed to understand natural rates of petroleum generation, expulsion mechanisms of primary migration, thermal stability of crude oil, reaction kinetics of biomarker transformations, and thermal maturity indicators in sedimentary basins.

Geochimica et Cosmochimica Acta↗

USGS1999

D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310–381°C), time (12–144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil–hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330°C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ≈ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381°C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350°C for 72 h, or 330°C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115°C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected by exchange with water hydrogen at typical reservoir conditions over geologic time. It will be difficult to utilize D/H ratios of thermally mature bulk or fractions of organic matter to quantitatively reconstruct isotopic aspects of paleoclimate and paleoenvironment. Hope resides in compound-specific D/H ratios of thermally stable, extractable biomarkers (“molecular fossils”) that are less susceptible to hydrogen exchange with water-derived hydrogen.

Geochimica et Cosmochimica Acta↗