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At least 145 records · Page 8Linked to original sources

Transcriptome signatures of wastewater effluent exposure in larval zebrafish vary with seasonal mixture composition in an effluent-dominated stream

Wastewater treatment plant (WWTP) effluent-dominated streams provide critical habitat for aquatic and terrestrial organisms but also continually expose them to complex mixtures of pharmaceuticals that can potentially impair growth, behavior, and reproduction. Currently, few biomarkers are available that relate to pharmaceutical-specific mechanisms of action. In the experiment reported in this paper, zebrafish ( Danio rerio ) embryos at two developmental stages were exposed to water samples from three sampling sites (0.1 km upstream of the outfall, at the effluent outfall, and 0.1 km below the outfall) during base-flow conditions from two months (January and May) of a temperate-region effluent-dominated stream containing a complex mixture of pharmaceuticals and other contaminants of emerging concern. RNA-sequencing identified potential biological impacts and biomarkers of WWTP effluent exposure that extend past traditional markers of endocrine disruption. Transcriptomics revealed changes to a wide range of biological functions and pathways including cardiac, neurological, visual, metabolic, and signaling pathways. These transcriptomic changes varied by developmental stage and displayed sensitivity to variable chemical composition and concentration of effluent, thus indicating a need for stage-specific biomarkers. Some transcripts are known to be associated with genes related to pharmaceuticals that were present in the collected samples. Although traditional biomarkers of endocrine disruption were not enriched in either month, a high estrogenicity signal was detected upstream in May and implicates the presence of unidentified chemical inputs not captured by the targeted chemical analysis. This work reveals associations between bioeffects of exposure, stage of development, and the composition of chemical mixtures in effluent-dominated surface water. The work underscores the importance of measuring effects beyond the endocrine system when assessing the impact of bioactive chemicals in WWTP effluent and identifies a need for non-targeted chemical analysis when bioeffects are not explained by the targeted analysis.

Iowa↗

Sex assignment of lake sturgeon (Acipenser fluvescens) based on plasma sex hormone and vitellogenin levels

This study focused on identifying the sex of lake sturgeon by measuring the sex hormones estradiol and testosterone, and the phosphoprotein vitellogenin (Vtg) in blood plasma by radioimmunoassay and enzyme-linked immunosorbent assay, respectively, and evaluating these techniques as tools in lake sturgeon population management. Surveys of the St Clair River (SCR) lake sturgeon population have characterized it as rebounding by having steady or increasing recruitment since 1997. However, researchers have not been able to effectively determine the sex for most of the sturgeon they capture because few fish caught during surveys are releasing gametes. A total of 115 fish were sampled from May through June in 2004 and 2005 from the SCR, Michigan, USA. Of these, only four females and eight males were verified (i.e. they were releasing gametes at time of capture), resulting in very few fish with which to validate blood hormone and Vtg biomarkers of sex. Fifty-six percent of the fish were assigned a sex designation based on biomarker criteria. Correspondence between actual gonadal sex and biomarker-directed classification was good for the small subset of fish for which gonadal sex was definitively determined. Moreover, application of the steroid values in a predictive sex assignment model developed for white sturgeon misclassified only the same two fish that were misclassified with the steroid and Vtg biomarkers. The experimental results suggest a sex ratio of 1 : 2.7 (F:M), however more conclusive methods are needed to confirm this ratio because so few fish were available for sex validation. Of the 43 males, 14 were within the legal slot limit, 11 were smaller than 1067 mm total length (TL), and 18 were larger than 1270 mm TL. All 15 females were larger than 1270 mm TL, and thus protected by the slot limit criteria. Considering that lake sturgeon are threatened in Michigan, an advantage to using blood plasma assays was that fish were not harmed, and sample collection was quick, simple, and inexpensive. However, because a sufficiently large number of fish could not be validated for gonadal sex due to handling restrictions given the fish's protected status, assignment of sex is not based on a robust multi-variate model. An immediate alternative may be to use other non-invasive field methods (e.g. ultrasound, fiber-optic endoscope) to provide a more timely classification while establishing well-validated plasma hormone and Vtg-based predictive models for sex assignment of lake sturgeon. ?? 2009 Blackwell Verlag, Berlin.

Conference Paper↗

Non-lethal assessment of freshwater mussel physiological response to changes in environmental factors

The development of effective nonlethal biomonitoring techniques is imperative for the preservation of imperiled freshwater mussel populations. Changes in hemolymph chemistry profiles and tissue glycogen are potential biomarkers for nonlethally monitoring stress in mussels. We sampled three species in the Flint River Basin over 2 years to evaluate how these hemolymph and tissue biomarkers responded to environmental changes. We used hierarchical linear models to evaluate the relationships between variation in the biomarkers and environmental factors and found that the responses of the hemolymph and tissue parameters were strongly related to stream discharge. Shifts in alanine aminotransferase and glycogen showed the largest relations with discharge at the time of sampling, while magnesium levels were most explained by the discharge for 5 days prior to sampling. Aspartate aminotransferase, bicarbonate, and calcium showed the strongest relations with mean discharge for 15 days prior to sampling. The modeling results indicated that biomarker responses varied substantially among individuals of different size, sex, and species and illustrated the value of hierarchical modeling techniques to account for the inherent complexity of aquatic ecosystems.

Canadian Journal of Fisheries and Aquatic Sciences↗

Oil and gas geochemistry and petroleum systems of the Fort Worth Basin

Detailed biomarker and light hydrocarbon geochemistry confirm that the marine Mississippian Barnett Shale is the primary source rock for petroleum in the Fort Worth Basin, north-central Texas, although contributions from other sources are possible. Biomarker data indicate that the main oil-generating Barnett Shale facies is marine and was deposited under dysoxic, strong upwelling, normal salinity conditions. The analysis of two outcrop samples and cuttings from seven wells indicates variability in the Barnett Shale organic facies and a possibility of other oil subfamilies being present. Light hydrocarbon analyses reveal significant terrigenous-sourced condensate input to some reservoirs, resulting in terrigenous and mixed marine-terrigenous light hydrocarbon signatures for many oils. The light hydrocarbon data suggest a secondary, condensate-generating source facies containing terrigenous or mixed terrigenous-marine organic matter. This indication of a secondary source rock that is not revealed by biomarker analysis emphasizes the importance of integrating biomarker and light hydrocarbon data to define petroleum source rocks. Gases in the Fort Worth Basin are thermogenic in origin and appear to be cogenerated with oil from the Barnett Shale, although some gas may also originate by oil cracking. Isotope data indicate minor contribution of biogenic gas. Except for reservoirs in the Pennsylvanian Bend Group, which contain gases spanning the complete range of observed maturities, the gases appear to be stratigraphically segregated, younger reservoirs contain less mature gas, and older reservoirs contain more mature gas. We cannot rule out the possibility that other source units within the Fort Worth Basin, such as the Smithwick Shale, are locally important petroleum sources. Copyright ?? 2007. The American Association of Petroleum Geologists. All rights reserved.

American Association of Petroleum Geologists Bulle↗

Biomonitoring of Environmental Status and Trends (BEST) Program: Environmental contaminants and their effects on fish in the Mississippi River Basin

We collected, examined, and analyzed 1378 fish of 22 species from 47 sites in the Mississippi River basin (MRB) during 1995 and from a reference site in 1996. The sampling sites in the MRB represented National Contaminant Biomonitoring Program (NCBP) stations situated at key points on major rivers and National Water- Quality Assessment Program (NAWQA) stations located on lower-order rivers and streams in the Eastern Iowa Basins (EIB) and Mississippi Embayment (MSE) Study Units. The reference site was the water supply system of the USGS-Leetown Science Center in rural Jefferson County, WV. Common carp (Cyprinus carpio; carp) and black basses (Micropterus spp.; bass), the targeted species, together represented 82% of the fish collected. Each fish was examined in the field for externally and internally visible gross lesions, selected organs were weighed to compute various ponderal and organo-somatic indices, and selected tissues and fluids were obtained and preserved for analysis of biomarkers. Fish health indicators included splenic macrophage aggregates, lysozyme activity, and hispathological analysis of liver, kidney, and other tissues. Reproductive biomarkers included analysis of plasma concentrations of vitellogenin (vtg) and the sex steroid hormones 17-estradiol (E2) and 11-ketotestosterone (11- kt); and the histological determination of percent oocyte atresia (in female fish) and gonadal stage. Hepatic ethoxyresorufin O-deethylase (EROD) activity was also measured. Composite samples of whole fish from each station were grouped by species and gender and analyzed for persistent organochlorine and elemental contaminants and for dioxin-like activity (TCDD-EQ) using the H4IIE rat hepatoma cell bioassay. Organochlorine and inorganic contaminant concentrations in fish were generally low relative to historical levels at most sites, but remained present at concentrations representing threats to piscivorous wildlife in some locations. Toxaphene and DDT (mostly as p,p?-DDE) concentrations remained elevated in fish from the cottongrowing regions of the lower Mississippi valley, and were generally greater in the smaller streams draining agricultural areas (that is, in the MSE Study Unit) than at large river sites. Cyclodiene pesticide concentrations were also greatest in the EIB Study Unit and elsewhere in the corn-growing regions of the mid-MRB. Former point-sources of organochlorine pesticides also remained evident, especially in the Mississippi River near Memphis, TN. Consistent with previous findings, total PCB concentrations tended to be greatest (1-3 g/g) in the industrialized and urbanized Ohio River and Upper Mississippi sub-basins and at Memphis, TN, and were generally correlated with TCDD-EQ and EROD activity. Conversely, PCB concentrations were low (<0.1 g/g) in the more agricultural parts of the MRB. Concentrations of inorganic contaminants were also relatively low and stable or declining relative to past levels at most sites. Exceptions were Hg and Se; Hg concentrations were slightly elevated (>0.3 g/g) in bass from the Mississippi River at Memphis and several other sites and in carp from one MSE site. Concentrations of Se were also great enough to constitute a hazard to piscivorous wildlife (>0.6 g/g) at several MRB sites in the western parts of the MRB and were especially high (4-5 g/g) in fish from John Martin Reservoir, CO, where elevated concentrations were reported previously. Biomarker results indicated that fish from many stations had been exposed to contaminants, but at no sites did findings indicate exposure to high concentrations of toxic chemicals. Noteworthy among biomarker findings was that 73% of the male smallmouth bass (Micropterus dolomieui) from the Mississippi River at Lake City, MN (Lake Pepin) were intersex as indicated by the histological detection of ovotestes; and the combined EROD and H4IIE results indicated that fish from several rural sites in the

Mississippi River basin↗

Effects of Bromus tectorum invasion on microbial carbon and nitrogen cycling in two adjacent undisturbed arid grassland communities

Soil nitrogen (N) is an important component in maintaining ecosystem stability, and the introduction of non-native plants can alter N cycling by changing litter quality and quantity, nutrient uptake patterns, and soil food webs. Our goal was to determine the effects of Bromus tectorum (C 3 ) invasion on soil microbial N cycling in adjacent non-invaded and invaded C 3 and C 4 native arid grasslands. We monitored resin-extractable N, plant and soil δ 13 C and δ 15 N, gross rates of inorganic N mineralization and consumption, and the quantity and isotopic composition of microbial phospholipid biomarkers. In invaded C 3 communities, labile soil organic N and gross and net rates of soil N transformations increased, indicating an increase in overall microbial N cycling. In invaded C 4 communities labile soil N stayed constant, but gross N flux rates increased. The δ 13 C of phospholipid biomarkers in invaded C 4 communities showed that some portion of the soil bacterial population preferentially decomposed invader C 3 -derived litter over that from the native C 4 species. Invasion in C 4 grasslands also significantly decreased the proportion of fungal to bacterial phospholipid biomarkers. Different processes are occurring in response to B. tectorum invasion in each of these two native grasslands that: 1) alter the size of soil N pools, and/or 2) the activity of the microbial community. Both processes provide mechanisms for altering long-term N dynamics in these ecosystems and highlight how multiple mechanisms can lead to similar effects on ecosystem function, which may be important for the construction of future biogeochemical process models.

Biogeochemistry↗

Individual variability in esterase activity and CYP1A levels in Chinook salmon (Oncorhynchus tshawytscha) exposed to esfenvalerate and chlorpyrifos

Acetylcholinesterase (AChE) activity has traditionally been monitored as a biomarker of organophosphate (OP) and/or carbamate exposure. However, AChE activity may not be the most sensitive endpoint for these agrochemicals, because OPs can cause adverse physiological effects at concentrations that do not affect AChE activity. Carboxylesterases are a related family of enzymes that have higher affinity than AChE for some OPs and carbamates and may be more sensitive indicators of environmental exposure to these pesticides. In this study, carboxylesterase and AChE activity, cytochrome P4501A (CYP1A) protein levels, and mortality were measured in individual juvenile Chinook salmon (Oncorhynchus tshawytscha) following exposure to an OP (chlorpyrifos) and a pyrethroid (esfenvalerate). As expected, high doses of chlorpyrifos and esfenvalerate were acutely toxic, with nominal concentrations (100 and 1 ??g/l, respectively) causing 100% mortality within 96 h. Exposure to chlorpyrifos at a high dose (7.3 ??g/l), but not a low dose (1.2 ??g/l), significantly inhibited AChE activity in both brain and muscle tissue (85% and 92% inhibition, respectively), while esfenvalerate exposure had no effect. In contrast, liver carboxylesterase activity was significantly inhibited at both the low and high chlorpyrifos dose exposure (56% and 79% inhibition, respectively), while esfenvalerate exposure still had little effect. The inhibition of carboxylesterase activity at levels of chlorpyrifos that did not affect AChE activity suggests that some salmon carboxylesterase isozymes may be more sensitive than AChE to inhibition by OPs. CYP1A protein levels were ???30% suppressed by chlorpyrifos exposure at the high dose, but esfenvalerate had no effect. Three teleost species, Chinook salmon, medaka (Oryzias latipes) and Sacramento splittail (Pogonichthys macrolepidotus), were examined for their ability to hydrolyze a series of pyrethroid surrogate substrates and in all cases hydrolysis activity was undetectable. Together these data suggest that (1) carboxylesterase activity inhibition may be a more sensitive biomarker for OP exposure than AChE activity, (2) neither AChE nor carboxylesterase activity are biomarkers for pyrethroid exposure, (3) CYP1A protein is not a sensitive marker for these agrochemicals and (4) slow hydrolysis rates may be partly responsible for acute pyrethroid toxicity in fish. ?? 2005 Elsevier B.V. All rights reserved.

Aquatic Toxicology↗

The genomic transcriptional response of female fathead minnows ( Pimephales promelas ) to an acute exposure to the androgen, 17β-trenbolone

We investigated the genomic transcriptional response of female fathead minnows (Pimephales promelas) to an acute (4 days) exposure to 0.1 or 1.0 ??g/L of 17??-trenbolone (TB), the active metabolite of an anabolic androgenic steroid used as a growth promoter in cattle and a contaminant of concern in aquatic systems. Our objectives were to investigate the gene expression profile induced by TB, define biomarkers of exposure to TB, and increase our understanding of the mechanisms of adverse effects of TB on fish reproduction. In female gonad tissue, microarray analysis using a 22 K oligonucleotide microarray (EcoArray Inc., Gainesville, FL) showed 99 significantly upregulated genes and 741 significantly downregulated genes in response to 1 ??g TB/L. In particular, hydroxysteroid (17??) dehydrogenase 12a (hsd17b12a), zona pellucida glycoprotein 2.2 (zp2.2), and protein inhibitor of activated STAT, 2 (pias2) were all downregulated in gonad. Q-PCR measurements in a larger sample set were consistent with the microarray results in the direction and magnitude of these changes in gene expression. However, several novel potential biomarkers were verified by Q-PCR in the same samples, but could not be validated in independent samples. In liver, Q-PCR measurements showed a significant decrease in vitellogenin 1 (vtg1) mRNA expression. In brain, cytochrome P450, family 19, subfamily A, polypeptide 1b (cyp19a1b, previously known as aromatase B) transcript levels were significantly reduced following TB exposure. Our study provides a candidate gene involved in mediating the action of TB, hsd17b12a, and two potential biomarkers sensitive to acute TB exposure, hepatic vtg1 and brain cyp19a1b.

Aquatic Toxicology↗

Molecular indicators of methane metabolisms at cold seeps along the United States Atlantic margin

A lipid biomarker study was undertaken to determine the microbial composition and variability in authigenic carbonates and associated soft bottom habitats from the Norfolk and the Baltimore Canyon seep fields along the US mid-Atlantic margin. Results from this study capture a distinct molecular signal from methane oxidizing archaea, including archaeol (I), sn-2-hydroxyarchaeol, pentamethylicosane (PMI), and crocetane. These consortia of methane-oxidizing Archaea have been identified as carrying out anaerobic oxidation of methane (AOM), thereby favoring the precipitation of methane derived authigneic carbonates. The carbon isotope (δ13C) values of AOM-related lipids were strongly depleted in 13C, (i.e., archaeol: -91.64 ‰, sn-2-hydroxyarchaeol: -129.18 ‰, pentamethylicosane (PMI); -131.36 ‰, and crocetane: -70.94 ‰), confirming the dominance of methane as the dominant carbon source for the Archaea during AOM fractionation. The presence of terminally branched fatty acids such as the antesio- and iso-C15:0 components, diagnostic of sulfate-reducing bacteria (SRB), and their depleted δ13C signature (-107.6 ‰), supports syntrophy of SRB with methane-oxidizing archaea. While lipid biomarker profiles of authigenic carbonates biomarker are similar to those found in the seep sediment, suggesting a similar microbial assemblage within the seep-microbiome, a range in lipid composition, distribution, and isotopic signature between seep sites and matrix type suggests AOM is performed by multiple archaeal sources, instead of a single archaeal species.

Atlantic margin↗

Chemical contamination of the Rybinsk Reservoir, northwest Russia: Relationship between liver polychlorinated biphenyls (PCB) content and health indicators in bream (Abramis brama)

The Rybinsk Reservoir (Russia) is the largest artificial waterbody in Europe (4550 km 2 ) and provides drinking water for population of the cities located along the coast line. Industrialization in Cherepovets at the northeastern portion of the reservoir, including one of the largest metallurgical facilities in Europe, has resulted in chemical contamination of the reservoir. The extent of polychlorinated biphenyls (PCB) contamination in bream liver, a common fish species, taken from six locations in the Rybinsk Reservoir and Volga River, and biochemical and morphometric biomarkers of fish health were investigated. Liver PCB concentrations ranged from non-detected to 3.4 &mu;g/g wet wt of liver, with the greatest concentrations found in fish taken near the industrialized area in Sheksna Reach of Rybinsk Reservoir. The source of the bream contamination is the PCB pollution of bottom organisms and sediments conditioned with industrialization facilities of Cherepovets. The patterns of the PCB congeners in the livers of bream taken near Cherepovets were similar at all of the stations that were sampled around the reservoir and Volga River. Among the common fish health biomarkers used only liver total ChE activity and liver-somatic index in bream near Cherepovets can reflect environmental pollution. Other morphometric (FCF, Clark&rsquo;s condition factors, and spleen-somatic index) and biochemical (protein content and acetylcholinesterase activity in the brain) biomarkers related with fish health varied among locations, but were not correlated to the concentrations of PCBs in the bream livers.

Rybinsk Reservoir↗

Differentiating persistent and intermittent euxinia from the molecular derivatives of green sulfur bacteria carotenoids

Green sulfur bacteria biomarkers that indicate euxinia within the photic zone sometimes co-occur with evidence of contradictory depositional redox conditions, such as oxygen-requiring fossils or bioturbation. Intermittent euxinia may explain this apparent contradiction, and recent studies of modern environments show that green sulfur bacteria dwell in transiently euxinic settings. As a result, new approaches are needed to distinguish green sulfur bacteria biomarkers indicative of persistent versus intermittent euxina in ancient sedimentary samples, which this study addresses by investigating how the distribution of isorenieratene derivatives relates to depositional redox conditions. To accomplish this objective, this study focuses on two drill cores through the Upper Cretaceous Mowry Shale and the Eagle Ford Group. These drill cores are comparably thermally immature according to vitrinite reflectance data, and these formations in these cores capture a spectrum of depositional redox conditions according to multiple organic and inorganic proxies, including newly acquired iron speciation and kerogen organic sulfur data. The results presented here reveal that higher molecular weight diagenetic products of isorenieratene are preferentially preserved under persistent euxinia compared to intermittently euxinic intervals that contain isorenieratene derivatives that are shifted to lower molecular weights. Further, the total inventory of aromatic carotenoid diagenetic products contains features that can be used to identify green sulfur bacteria biomarkers from reworked petrogenic sources. Accordingly, the diagenetic fate of isorenieratene and the distribution of its diagenetic products distinguish persistent versus intermittent euxinia, which can be used to sharpen our evaluation of euxinia in the geologic record.

Geochemica et Cosmochimica Acta↗

Geochemical advances in Arctic Alaska oil typing - North Slope oil correlation and charge history

The Arctic Alaska petroleum province is geologically and geochemically complex. Mixed hydrocarbon charge from multiple source rocks and/or levels of thermal maturity is common within an individual oil pool. Biomarker and chemometric statistical analyses were used to correlate twenty-nine oils to five oil families derived from: (1) Triassic Shublik Formation (calcareous organofacies), (2) Triassic Shublik Formation (shaly organofacies), (3) Jurassic Kingak Shale, (4) Cretaceous shale (pebble shale unit and Hue Shale), and (5) Paleogene shale (Canning Formation). Age-diagnostic and source-related oil biomarker parameters establish clear genetic relationships between the normal oil-window components and their putative source designations. However, application of diamondoid analyses reveals mixed-oil accumulations with postmature charge contributions (diamondoid-rich and biomarker-poor) in many oils. Most sampled reservoirs contain a predominant charge derived from a single oil-window source plus a minor contribution from one or more higher maturity source(s). Variations in source organofacies also are recognized in the Shublik, Kingak, and Cretaceous oil families. In some cases, oils from multiple pools within a single field display relatively homogeneous geochemical profiles, suggesting a common source and migration pathway. For example, oil from the significant Pikka discovery is inferred to originate mainly from the calcareous Shublik Formation. In other cases, variability among oils from multiple pools within a single field (e.g., Milne Point, Colville River, and Northstar) likely indicates a more complex source, migration, and charge history. Results may be useful for anticipating the composition of oil charge in stratigraphic traps with low-permeability sandstone reservoirs, where oil gravity and other chemical parameters may influence economic viability.

Alaska↗

Geochemical characterization of tarballs on beaches along the California coast. Part I - Shallow seepage impacting the Santa Barbara Channel Islands, Santa Cruz, Santa Rosa and San Miguel

Tarballs are common along the southern California coastline. This study investigates tarballs from beaches along this coastline, with a focus on Santa Cruz, Santa Rosa, and San Miquel Islands in the Santa Barbara Channel. The tarballs were fingerprinted using biomarker and stable carbon isotope parameters, and then grouped according to genetic similarities. The data show that the tarballs are of natural and not anthropogenic origin and that all originate from source rock within the Miocene Monterey Formation via shallow seeps offshore. Sterane biomarker parameters were found to vary widely in the sample set. Biodegradation, especially of the regular steranes, is the primary process impacting the biomarker distributions in a large group of samples. The most common tarball occurrences appear to come from offshore seepage near the west end of Santa Cruz Island. Another major group most likely was transported north from near Santa Monica Bay. Several individual occurrences of some of these tarball groups also were found on beaches as far north as Pt. Reyes and as far south as San Diego, indicating significant long-distance dispersal by ocean currents. This study begins a library of tarball fingerprints to be used as a database to help distinguish between natural and anthropogenic tar occurrences all along the California coast, and to compare shallow seepage with future samples of deeper production oils from the same area.

Organic Geochemistry↗

De-convoluting mixed crude oil in Prudhoe Bay Field, North Slope, Alaska

Seventy-four crude oil samples from the Barrow arch on the North Slope of Alaska were studied to assess the relative volumetric contributions from different source rocks to the giant Prudhoe Bay Field. We applied alternating least squares to concentration data (ALS-C) for 46 biomarkers in the range C19-C35 to de-convolute mixtures of oil generated from carbonate rich Triassic Shublik Formation and clay rich Jurassic Kingak Shale and Cretaceous Hue Shale-gamma ray zone (Hue-GRZ) source rocks. ALS-C results for 23 oil samples from the prolific Ivishak Formation reservoir of the Prudhoe Bay Field indicate approximately equal contributions from Shublik Formation and Hue-GRZ source rocks (37% each), less from the Kingak Shale (26%), and little or no contribution from other source rocks. These results differ from published interpretations that most oil in the Prudhoe Bay Field originated from the Shublik Formation source rock. With few exceptions, the relative contribution of oil from the Shublik Formation decreases, while that from the Hue-GRZ increases in reservoirs along the Barrow arch from Point Barrow in the northwest to Point Thomson in the southeast (???250 miles or 400 km). The Shublik contribution also decreases to a lesser degree between fault blocks within the Ivishak pool from west to east across the Prudhoe Bay Field. ALS-C provides a robust means to calculate the relative amounts of two or more oil types in a mixture. Furthermore, ALS-C does not require that pure end member oils be identified prior to analysis or that laboratory mixtures of these oils be prepared to evaluate mixing. ALS-C of biomarkers reliably de-convolutes mixtures because the concentrations of compounds in mixtures vary as linear functions of the amount of each oil type. ALS of biomarker ratios (ALS-R) cannot be used to de-convolute mixtures because compound ratios vary as nonlinear functions of the amount of each oil type.

Organic Geochemistry↗

Historical changes in organic matter input to the muddy sediments along the Zhejiang-Fujian Coast, China over the past 160 years

The burial of sedimentary organic matter (SOM) in the large river-influenced estuarine-coastal regions is affected by hydrodynamic sorting, diagenesis and human activities. Typically, the inner shelf region of the East China Sea is a major carbon sink of the Yangtze River-derived fine-grained sediments. Most of the previous work concentrated on the studies of surface sediments or used a single-proxy in this region. In this study, two cores from the Zhejiang-Fujian Coast were analyzed using bulk (TOC, TN and δ 13 C TOC ) and molecular biomarker ( n -alkane, brassicasterol, dinosterol and glycerol dialkyl glycerol tetraether lipids) techniques to clarify the sources, spatiotemporal distribution and fate of SOM in the Yangtze River Estuary and adjacent shelf. Results from this study indicated that the effects of diagenesis and diffusion on different sedimentary biomarkers resulted in overestimation of the relative contribution of terrestrial organic matter (%OM terr ), compared with those based on δ 13 C TOC . The amounts of terrestrial plant organic matter (OM plant ) and%OM terr in sediments decreased offshore. In contrast, the amounts of marine organic matter (OM marine ) increased offshore, but closer to the Yangtze River mouth, the amounts of soil organic matter (OM soil ) increased. Moreover, the amounts of TOC, OM plant and OM marine biomarkers increased, but OM soil and%OM terr decreased over time in recent decades. Our study suggests that spatial organic matter distribution patterns in marine shelf sediments were controlled primarily by hydrodynamic sorting and nutrient concentrations, and temporally diverse patterns were controlled predominantly by anthropogenic influence (e.g., dam construction and soil conservation, reclamation and agricultural plantations, anthropogenic nutrient input, dust storms, eutrophication, etc) and climate events (e.g., interdecadal climatic jump and heavy rain events) in the geological period.

Zhejiang-Fujian Coast↗

Long-term assessment of relationships between changing environmental conditions and the physiology of southern Beaufort Sea polar bears (Ursus maritimus)

Climate change is influencing polar bear ( Ursus maritimus ) habitat, diet, and behavior but the effects of these changes on their physiology is not well understood. Blood-based biomarkers are used to assess the physiologic health of individuals but their usefulness for evaluating population health, especially as it relates to changing environmental conditions, has rarely been explored. We describe links between environmental conditions and physiologic functions of southern Beaufort Sea polar bears using data from blood samples collected from 1984 to 2018, a period marked by extensive environmental change. We evaluated associations between 13 physiologic biomarkers and circumpolar (Arctic oscillation index) and regional (wind patterns and ice-free days) environmental metrics and seasonal and demographic co-variates (age, sex, season, and year) known to affect polar bear ecology. We observed signs of dysregulation of water balance in polar bears following years with a lower annual Arctic oscillation index. In addition, liver enzyme values increased over time, which is suggestive of potential hepatocyte damage as the Arctic has warmed. Biomarkers of immune function increased with regional-scale wind patterns and the number of ice-free days over the Beaufort Sea continental shelf and were lower in years with a lower winter Arctic oscillation index, suggesting an increased allocation of energetic resources for immune processes under these conditions. We propose that the variation in polar bear immune and metabolic function is likely indicative of physiologic plasticity, a response that allows polar bears to remain in homeostasis even as they experience changes in nutrition and habitat in response to changing environments.

Alaska↗

Bioindicators of contaminant exposure and effect in aquatic and terrestrial monitoring

Bioindicators of contaminant exposure presently used in environmental monitoring arc discussed. Some have been extensively field-validated and arc already in routine application. Included are (1) inhibition of brain or blood cholinesterase by anticholinesterase pesticides, (2) induction of hepatic microsomal cytochromes P450 by chemicals such as PAHs and PCBs, (3) reproductive problems such as terata and eggshell thinning, and (4) aberrations of hemoglobin synthesis, including the effects of lead and of certain chlorinated hydrocarbons. Many studies on DNA damage and of histopathological effects, particularly in the form of tumors, have already been completed. There are presently numerous other opportunities for field validation. Bile metabolites of contaminants in fish reveal exposure to contaminants that might otherwise be difficult to detect or quantify. Bile analysis is beginning to be extended to species other than fishes. Assessment of oxidative damage and immune competence appear to be valuable biomarkers. needing only additional field validation for wider use. The use of metallothioneins as biomarkers depends on the development of convenient, inexpensive methodology that provides information not available from measurements of metal ions. The use of stress proteins as biomarkers depends on development of convenient, inexpensive methodology and field validation. Gene arrays and proteomics hold promise as bioindicators for contaminant exposure or effect, particularly because of the large amount of data that could be generated, but they still need extensive development and testing.

Book chapter↗

Natural offshore oil seepage and related tarball accumulation on the California coastline — Santa Barbara Channel and the southern Santa Maria Basin; source identification and inventory

Oil spillage from natural sources is very common in the waters of southern California. Active oil extraction and shipping is occurring concurrently within the region and it is of great interest to resource managers to be able to distinguish between natural seepage and anthropogenic oil spillage. The major goal of this study was to establish the geologic setting, sources, and ultimate dispersal of natural oil seeps in the offshore southern Santa Maria Basin and Santa Barbara Basins. Our surveys focused on likely areas of hydrocarbon seepage that are known to occur between Point Arguello and Ventura, California. Our approach was to 1) document the locations and geochemically fingerprint natural seep oils or tar; 2) geochemically fingerprint coastal tar residues and potential tar sources in this region, both onshore and offshore; 3) establish chemical correlations between offshore active seeps and coastal residues thus linking seep sources to oil residues; 4) measure the rate of natural seepage of individual seeps and attempt to assess regional natural oil and gas seepage rates; and 5) interpret the petroleum system history for the natural seeps. To document the location of sub-sea oil seeps, we first looked into previous studies within and near our survey area. We measured the concentration of methane gas in the water column in areas of reported seepage and found numerous gas plumes and measured high concentrations of methane in the water column. The result of this work showed that the seeps were widely distributed between Point Conception east to the vicinity of Coal Oil Point, and that they by in large occur within the 3-mile limit of California State waters. Subsequent cruises used sidescan and high resolution seismic to map the seafloor, from just south of Point Arguello, east to near Gaviota, California. The results of the methane survey guided the exploration of the area west of Point Conception east to Gaviota using a combination of seismic instruments. The seafloor was mapped by sidescan sonar, and numerous lines of high -resolution seismic surveys were conducted over areas of interest. Biomarker and stable carbon isotope ratios were used to infer the age, lithology, organic matter input, and depositional environment of the source rocks for 388 samples of produced crude oil, seep oil, and tarballs mainly from coastal California. These samples were used to construct a chemometric fingerprint (multivariate statistics) decision tree to classify 288 additional samples, including tarballs of unknown origin collected from Monterey and San Mateo County beaches after a storm in early 2007. A subset of 9 of 23 active offshore platform oils and one inactive platform oil representing a few oil reservoirs from the western Santa Barbara Channel were used in this analysis, and thus this model is not comprehensive and the findings are not conclusive. The platform oils included in this study are from west to east: Irene, Hildago, Harvest, Hermosa, Heritage, Harmony, Hondo, Holly, Platform A, and Hilda (now removed). The results identify three “tribes” of 13 C-rich oil samples inferred to originate from thermally mature equivalents of the clayey-siliceous, carbonaceous marl, and lower calcareous-siliceous members of the Monterey Formation. Tribe 1 contains four oil families having geochemical traits of clay-rich marine shale source rock deposited under suboxic conditions with substantial higher-plant input. Tribe 2 contains four oil families with intermediate traits, except for abundant 28,30-bisnorhopane, indicating suboxic to anoxic marine marl source rock with hemipelagic input. Tribe 3 contains five oil families with traits of distal marine carbonate source rock deposited under anoxic conditions with pelagic but little or no higher-plant input. Tribes 1 and 2 occur mainly south of Point Conception in paleogeographic settings where deep burial of the Monterey Formation source rock favored generation from all three members or their equivalents. In this area, oil from the clayey-siliceous and carbonaceous marl members (Tribes 1 and 2) may overwhelm that from the lower calcareous-siliceous member (Tribe 3) because the latter is thinner and less oil-prone than the overlying members. Tribe 3 occurs mainly north of Point Conception, where shallow burial caused preferential generation from the underlying lower calcareous-siliceous member or another unit with similar characteristics. It is very desirable to be able to clearly distinguish the naturally occurring seep oils from the anthropogenically derived platform oils. Within the “training set” of oils and tars (388 samples), the biomarker parameters are sometimes sufficient to allow unique discrimination of individual platform oils. More often however, platform samples and seep samples with sources geographically close to each other are too similar to each other, with respect to the biomarker parameters, to definitively differentiate them on that basis alone. In some cases other parameters can be helpful. These other parameters are related to the degree of biogeochemical degradation or weathering that the oils or tars have experienced. These components include the typical oil distribution of n-alkane hydrocarbons and isoprenoids pristane and phytane. All of the platform oils in our sample set contain these components. On the other hand, the seep oils or tars have been exposed to significant biodegradation while in the near subsurface. The majority, but not all of seep oils or tars have been biodegraded up to or beyond the loss of n-alkanes and isoprenoids. Seep oils found in the vicinity of Coal Oil Point or Arroyo Burro are apparently the least weathered and are particularly likely to retain significant n-alkanes and isoprenoids. Therefore the combination of chemometric fingerprinting and the presence or absence of n-alkanes and isoprenoids help to differentiate anthropogenic production oils versus natural seeps oils and tars. The differentiation is not always definitive because of the close chemical similarity of some samples and the variability in the biodegradation progression. This is the case near Coal Oil Point, and near Platform A (Dos Cuadros Field) where seep oils and Platform Holly and Platform A oils are genetically very similar and cannot be definitively distinguished after a period of a few days of weathering. In contrast, oils from the Point Conception platforms can be distinguished on the basis of chemometric fingerprinting alone. In the middle of this spectrum are oils from Platforms Harmony, Heritage, and Hondo, where it is expected that oil weathering would take on the order of two weeks to a month to produce tarballs similar to those seen near Point Conception. In this case there is a much greater degree of weathering needed to proceed from produced oil to the biodegraded tar characteristic of tarball stranded on the beach. Tar deposition on beaches was monitored as part of cooperative with the County of Santa Barbara Energy Division and the U.S. Geological Survey during 2001-2003. We found tar deposition varies on a seasonal basis. In general, tarballs accumulate at a faster rate or remain longer on all beaches during the summer and fall months. The reasons for this are unclear based on our limited observations, however we speculate that factors such as prevailing winds and currents combined with more quiescent wave conditions favors the accumulation and preservation of tarballs on the beach during the summer and fall months. In contrast, winter storms, with much greater wave action remove beach sand and other materials, and stormy seas tend to break up oil that might weather into tarballs. Natural seepage is affected by the spring/neap tidal cycle; however, the link to tar deposition is unclear. Longer periods of monitoring are needed to address the variability in the data and provide a more robust statistical analysis.

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