Comprehensive Two-Dimensional Gas Chromatography in Petroleum Derived Samples: A Review on Advances in Source and Weathering Studies of Spilled Oil.

Since its introduction comprehensive two-dimensional gas chromatography (GC × GC) has been widely applied to analyze complex samples due to its enhanced peak capacity and selectivity, thereby increasing the number of identifiable peaks and improving coelution issues. Even though it is still undergoing development, GC × GC provides many advantages in the analysis of petroleum-derived samples, whether in reservoir geochemistry applications or in environmental studies associated with spilled oils. In general, it facilitates more thorough fingerprinting and compositional evaluation. In environmental studies, it helps enhance understanding of weathering processes and the environmental behavior of hydrocarbons, as its chromatographic retention indices can robustly estimate liquid vapor pressures, aqueous solubility and other physical chemical properties. This review presents a brief history of GC × GC instrumentation, discussing recent and significant advances in petroleum applications, from data handling techniques to reservoir geochemistry and environmental forensics, as well as some specific advantages achieved and certain limitations that continue to be encountered.

Simultaneous evaluation of benzotriazoles, benzothiazoles and benzenesulfonamides in water samples from the impacted urban Jacarepaguá Lagoon System (Rio de Janeiro, Brazil) by liquid chromatography coupled to electrospray tandem mass spectrometry.

Benzotriazoles, benzothiazoles, and benzenesulfonamides are emerging pollutants stable in aquatic media emitted by anthropogenic sources. Selected compounds of these classes were evaluated in the impacted urban Jacarepaguá Lagoon System (JLS) located in a tropical coastal region of Rio de Janeiro City, Brazil that has experienced a rapid expansion of urban occupation and environmental degradation in recent decades, and it represents a pioneering study of these compounds carried out in Brazilian areas. A method of solid phase extraction followed by ultra-performance liquid chromatography coupled to electrospray tandem mass-spectrometry was implemented to evaluate water samples collected in different water bodies (rivers, lagoons, and channels) of the JLS from March 2017 to May 2018. Limits of quantification (LOQs) ≤ 10.0 ng L-1, method linearity up to 1000 µg L-1, and recoveries between 62 and 121 % at three different levels were obtained. Individual concentrations varied from < LOQ to 5260 ng L-1 (benzotriazole, in May 2018) which also predominated in all river samples. 2-mercaptobenzothiazole predominated in samples taken in lagoons and channels in March 2017, and 2-aminobenzothiazole was never detected. River samples showed total concentrations up to 30 times larger in all sampling campaigns, except March 2017 when the sample taken at Tijuca Lagoon showed the largest total concentration of the compounds studied due to the largest concentration of 2-mercaptobenzothiazole (2505 ng L-1) found in this study. Principal component analysis (PCA) using only composition data was unable to distinguish samples from rivers, and lagoons and channels, but a PCA combining composition data and environmental parameters (pH, Eh, dissolved O2 concentration, temperature, salinity, and conductivity) discriminated the samples according to two groups: rivers and lagoons and channels. The Joá Channel flows directly to the open sea and our data allowed a (preliminary) estimation of the total mass flows of the studied compounds to the open sea, which would vary between 1702 g day-1 (March 2017) to 106 g day-1 (May 2018) and allowed a preliminary estimative based on the geometric mean of input of 87.9 kg year-1, indicating the importance of the drainage area to the contamination of the coastal area, and consequently to ocean pollution.

Evaluation of urban pollution in a tropical lacustrine ecosystem by using n-alkanes and sterols as biomarkers.

The Jacarepaguá Lagoon System (JLS) receives industrial and domestic waste in an urban area with high population density and intense economic activity. The hydrography of the lagoons favours the sedimentation of particulate material transferred from the drainage basin. Water engineering, such as channel dredging and subsea outfall, did not satisfactorily mitigate pollution effects. Therefore, the environment is highly eutrophic, presents frequent blooms of algae and generates high emissions of greenhouse gases. There is no record in the literature on the analysis of organic compounds in the water compartment. The present work applies sterols as biomarkers to quantify the degree of pollution caused by biogenic compounds in riverine and lacustrine water of the JLS. n-Alkanes were applied to estimate the fractions of petrogenic contaminants. The sums of n-alkanes and sterols analysed had average concentrations of 21 ± 20 µg L-1 and 10 ± 8 µg L-1, respectively, in the river samples and 235 ± 156 µg L-1 and 30 ± 28 µg L-1, respectively, in the lagoon samples. The work also showed that the organic compounds inside the lagoons are evenly distributed, and approximately 7% of them are transferred to the marine ecosystem. Biogenic biomarkers and the absolute concentrations of sterols showed that sewage contaminants transferred by the rivers are partially decomposed in the lagoons. The correlations between indices and physicochemical parameters indicated that the degradation of organic compounds in the lagoons occurs mainly in the sediment compartment under anoxic conditions. The indices for sewage indicate that the ecosystem has exceeded its carrying capacity. The indices based on n-alkanes reported strong contamination at all sampling stations and inferred that 75-100% of these compounds were derived from petrogenic sources. These indices did not show any difference between rivers and the lagoon, which demonstrates the resilience of these compounds in the ecosystem.

Linking eutrophication to carbon dioxide and methane emissions from exposed mangrove soils along an urban gradient.

Mangroves are one of the most important but threatened blue carbon ecosystems globally. Rapid urban growth has resulted in nutrient inputs and subsequent coastal eutrophication, associated with an enrichment in organic matter (OM) from algal and sewage sources and substantial changes in greenhouse gas (GHG) emissions. However, the effects of nitrogen (N) and phosphorus (P) enrichment on mangrove soil OM composition and GHG emissions, such as methane (CH4) and carbon dioxide (CO2), are still poorly understood. Here, we aim to evaluate the relationships between CO2 and CH4 efflux with OM composition in exposed soils from three mangrove areas along watersheds with different urbanization levels (Rio de Janeiro State, Brazil). To assess spatial (lower vs. upper intertidal zones) and seasonal (summer vs. winter) variability, we measured soil-air CO2 and CH4 fluxes at low spring tide, analyzing elementary (C, N, and P), isotopic (δ13C and δ15N), and the molecular (n-alkanes and sterols) composition of surface soil OM. A general trend of OM composition was found with increasing urban influence, with higher δ15N (proxy of anthropogenic N enrichment), less negative δ13C, more short-chain n-alkanes, lower C:N ratio (proxies of algal biomass), and higher epicoprostanol content (proxies of sewage-derived OM). The CO2 efflux from exposed soils increased greatly in median (25/75 % interquartile range) from 4.6 (2.9/8.3) to 24.0 (21.5/32.7) mmol m-2 h-1 from more pristine to more urbanized watersheds, independent of intertidal zone and seasonality. The CO2 fluxes at the most eutrophicated site were among the highest reported worldwide for mangrove soils. Conversely, CH4 emissions were relatively low (three orders of magnitude lower than CO2 fluxes), with high peaks in the lower intertidal zone during the rainy summer. Thus, our findings demonstrate the influence of coastal eutrophication on global warming potentials related to enhanced heterotrophic remineralization of blue carbon within mangrove soils.

Sterol and PAHs fingerprint analysis of organic matter at Southeast Brazilian Bay.

Southeast Brazilian bays have been increasingly degraded by untreated organic loads. Therefore, to assess fecal contamination status, sediment quality regarding polycyclic aromatic hydrocarbons (PAHs), and sources of organic matter (OM), we have determined fine-grained and total organic carbon (TOC) content and concentrations of PAHs and sterols in twenty-six surface sediment samples in Sepetiba Bay. The fine-grained (1-26 %), TOC (0.20-3.45 %), PAHs (

Greenhouse gas emissions (CO2 and CH4) and inorganic carbon behavior in an urban highly polluted tropical coastal lagoon (SE, Brazil).

Increasing eutrophication of coastal waters generates disturbances in greenhouse gas (GHG) concentrations and emissions to the atmosphere that are still poorly documented, particularly in the tropics. Here, we investigated the concentrations and diffusive fluxes of carbon dioxide (CO2) and methane (CH4) in the urban-dominated Jacarepagua Lagoon Complex (JLC) in Southeastern Brazil. This lagoonal complex receives highly polluted freshwater and shows frequent occurrences of anoxia and hypoxia and dense phytoplankton blooms. Between 2017 and 2018, four spatial surveys were performed (dry and wet conditions), with sampling in the river waters that drain the urban watershed and in the lagoon waters with increasing salinities. Strong oxygen depletion was found in the rivers, associated with extremely high values of partial pressure of CO2 (pCO2; up to 20,417 ppmv) and CH4 concentrations (up to 288,572 nmol L-1). These high GHG concentrations are attributed to organic matter degradation from untreated domestic effluents mediated by aerobic and anaerobic processes, with concomitant production of total alkalinity (TA) and dissolved inorganic carbon (DIC). In the lagoon, GHG concentrations decreased mainly due to dilution with seawater and degassing. In addition, the phytoplankton growth and CH4 oxidation apparently consumed some CO2 and CH4, respectively. TA concentrations showed a marked minimum at salinity of ~20 compared to the two freshwater and marine end members, indicating processes of re-oxidation of inorganic reduced species from the low-salinity region, such as ammonia, iron, and/or sulfides. Diffusive emissions of gases from the entire lagoon ranged from 22 to 48 mmol C m-2 d-1 for CO2 and from 2.2 to 16.5 mmol C m-2 d-1 for CH4. This later value is among the highest documented in coastal waters. In terms of global warming potential (GWP) and CO2 equivalent emissions (CO2-eq), the diffusive emissions of CH4 were higher than those of CO2. These results highlight that highly polluted coastal ecosystems are hotspots of GHG emissions to the atmosphere, which may become increasingly significant in future global carbon budgets.

Glacial-interglacial transitions in microbiomes recorded in deep-sea sediments from the western equatorial Atlantic.

In the late Quaternary, glacial-interglacial transitions are marked by major environmental changes. Glacial periods in the western equatorial Atlantic (WEA) are characterized by high continental terrigenous input, which increases the proportion of terrestrial organic matter (e.g. lignin, alkanes), nutrients (e.g. iron and sulphur), and lower primary productivity. On the other hand, interglacials are characterized by lower continental contribution and maxima in primary productivity. Microbes can serve as biosensors of past conditions, but scarce information is available on deep-sea sediments in the WEA. The hypothesis put forward in this study is that past changes in climate conditions modulated the taxonomic/functional composition of microbes from deep sediment layers. To address this hypothesis, we collected samples from a marine sediment core located in the WEA, which covered the last 130 kyr. This region is influenced by the presence of the Amazon River plume, which outputs dissolved and particulate nutrients in vast oceanic regions, as well as the Parnaiba river plume. Core GL-1248 was analysed by shotgun metagenomics and geochemical analyses (alkane, lignin, perylene, sulphur). Two clusters (glacial and interglacial-deglacial) were found based on taxonomic and functional profiles of metagenomes. The interglacial period had a higher abundance of genes belonging to several sub-systems (e.g. DNA, RNA metabolism, cell division, chemotaxis, and respiration) that are consistent with a past environment with enhanced primary productivity. On the other hand, the abundance of Alcanivorax, Marinobacter, Kangiella and aromatic compounds that may serve as energy sources for these bacteria were higher in the glacial. The glacial period was enriched in genes for the metabolism of aromatic compounds, lipids, isoprenoids, iron, and Sulphur, consistent with enhanced fluvial input during the last glacial period. In contrast, interglacials have increased contents of more labile materials originating from phytoplankton (e.g. Prochlorococcus). This study provides new insights into the microbiome as climatic archives at geological timescales.

Carbon accumulation rates recorded in the last 150years in tropical high mountain peatlands of the Atlantic Rainforest, SE - Brazil.

Peatlands are environmental matrices that store large amounts of organic carbon (TOC) and work as records of environmental changes. Recent record of organic carbon accumulated were assessed in two Forest National Parks, Itatiaia and Serra dos Órgãos in the Southeastern of Brazil. Based on organic and inorganic characterization, the cores from peatlands presented a predominance of organic material in an advanced stage of decomposition and those soils were classified as typical Haplosaprists Histosols. The combination of favorable topographic and climatic conditions led to rapid C accumulation across coastal mountain in the tropical peatlands studied, presenting an average accumulation rate of C, in the last century, of 194gCm-2yr-1 about 7 higher times than the rate found in boreal and subarctic peatlands, those higher values may be related to changes in the hydrological cycle occurred since 1950s.

Hydrological pulse regulating the bacterial heterotrophic metabolism between Amazonian mainstems and floodplain lakes.

We evaluated in situ rates of bacterial carbon processing in Amazonian floodplain lakes and mainstems, during both high water (HW) and low water (LW) phases (p < 0.05). Our results showed that bacterial production (BP) was lower and more variable than bacterial respiration, determined as total respiration. Bacterial carbon demand was mostly accounted by BR and presented the same pattern that BR in both water phases. Bacterial growth efficiency (BGE) showed a wide range (0.2-23%) and low mean value of 3 and 6%, (in HW and LW, respectively) suggesting that dissolved organic carbon was mostly allocated to catabolic metabolism. However, BGE was regulated by BP in LW phase. Consequently, changes in BGE showed the same pattern that BP. In addition, the hydrological pulse effects on mainstems and floodplains lakes connectivity were found for BP and BGE in LW. Multiple correlation analyses revealed that indexes of organic matter (OM) quality (chlorophyll-a, N stable isotopes and C/N ratios) were the strongest seasonal drivers of bacterial carbon metabolism. Our work indicated that: (i) the bacterial metabolism was mostly driven by respiration in Amazonian aquatic ecosystems resulting in low BGE in either high or LW phase; (ii) the hydrological pulse regulated the bacterial heterotrophic metabolism between Amazonian mainstems and floodplain lakes mostly driven by OM quality.

Amazon River carbon dioxide outgassing fuelled by wetlands.

River systems connect the terrestrial biosphere, the atmosphere and the ocean in the global carbon cycle. A recent estimate suggests that up to 3 petagrams of carbon per year could be emitted as carbon dioxide (CO2) from global inland waters, offsetting the carbon uptake by terrestrial ecosystems. It is generally assumed that inland waters emit carbon that has been previously fixed upstream by land plant photosynthesis, then transferred to soils, and subsequently transported downstream in run-off. But at the scale of entire drainage basins, the lateral carbon fluxes carried by small rivers upstream do not account for all of the CO2 emitted from inundated areas downstream. Three-quarters of the world's flooded land consists of temporary wetlands, but the contribution of these productive ecosystems to the inland water carbon budget has been largely overlooked. Here we show that wetlands pump large amounts of atmospheric CO2 into river waters in the floodplains of the central Amazon. Flooded forests and floating vegetation export large amounts of carbon to river waters and the dissolved CO2 can be transported dozens to hundreds of kilometres downstream before being emitted. We estimate that Amazonian wetlands export half of their gross primary production to river waters as dissolved CO2 and organic carbon, compared with only a few per cent of gross primary production exported in upland (not flooded) ecosystems. Moreover, we suggest that wetland carbon export is potentially large enough to account for at least the 0.21 petagrams of carbon emitted per year as CO2 from the central Amazon River and its floodplains. Global carbon budgets should explicitly address temporary or vegetated flooded areas, because these ecosystems combine high aerial primary production with large, fast carbon export, potentially supporting a substantial fraction of CO2 evasion from inland waters.

Particulate organic matter distribution along the lower Amazon River: addressing aquatic ecology concepts using fatty acids.

One of the greatest challenges in understanding the Amazon basin functioning is to ascertain the role played by floodplains in the organic matter (OM) cycle, crucial for a large spectrum of ecological mechanisms. Fatty acids (FAs) were combined with environmental descriptors and analyzed through multivariate and spatial tools (asymmetric eigenvector maps, AEM and principal coordinates of neighbor matrices, PCNM). This challenge allowed investigating the distribution of suspended particulate organic matter (SPOM), in order to trace its seasonal origin and quality, along a 800 km section of the Amazon river-floodplain system. Statistical analysis confirmed that large amounts of saturated FAs (15:0, 18:0, 24:0, 25:0 and 26:0), an indication of refractory OM, were concomitantly recorded with high pCO(2) in rivers, during the high water season (HW). Contrastingly, FAs marker which may be attributed in this ecosystem to aquatic plants (18:2ω6 and 18:3ω3) and cyanobacteria (16:1ω7), were correlated with higher O(2), chlorophyll a and pheopigments in floodplains, due to a high primary production during low waters (LW). Decreasing concentrations of unsaturated FAs, that characterize labile OM, were recorded during HW, from upstream to downstream. Furthermore, using PCNM and AEM spatial methods, FAs compositions of SPOM displayed an upstream-downstream gradient during HW, which was attributed to OM retention and the extent of flooded forest in floodplains. Discrimination of OM quality between the Amazon River and floodplains corroborate higher autotrophic production in the latter and transfer of OM to rivers at LW season. Together, these gradients demonstrate the validity of FAs as predictors of spatial and temporal changes in OM quality. These spatial and temporal trends are explained by 1) downstream change in landscape morphology as predicted by the River Continuum Concept; 2) enhanced primary production during LW when the water level decreased and its residence time increased as predicted by the Flood Pulse Concept.

Uso dos fenóis da lignina no estudo da matéria orgânica na várzea do Lago Grande Curuái, Pará e no Lago do Caçó, Maranhão, Brasil / Use of lignin phenols in the study of organic matter in the Lago Grande Curuái floodplain, Pará and Lake Caçó, Maranhão, Brazil

ste estudo tem por objetivo caracterizar os sedimentos superficiais, quanto ao seu teor e qualidade dos fenóis da lignina, em dois sistemas lacustres distintos: a Várzea do Lago Grande Curuái (PA) e o Lago do Caçó (MA). A Várzea do Lago Grande Curuái é localizada na margem direita do Rio Amazonas, aproximadamente 850 km da foz e é caracterizada pela presença de lagos de águas brancas e pretas. O Lago do Caçó está localizado no Maranhão, na borda do ecossistema amazônico. Foram realizadas análises da concentração de lignina (λ), carbono orgânico total (COT), nitrogênio e isótopos do carbono (δ13C). Os resultados indicam que os sedimentos superficias de lagos de águas brancas apresentam baixos valores de COT (1,5 a 3,6%), baixa concentração de λ (0,73 a 1,28 mg.100mg CO-1) e alto índice de degradação (0,29 a 2,01). Os sedimentos superficiais de lagos de águas pretas apresentam maiores valores de COT (6,0 a 12,1%) e de λ (1,44 a 1,93 mg.100mg CO-1) em relação aos sedimentos de lagos de águas brancas, porém baixos em comparação com os sedimentos do Lago do Caçó (7,2 ~ 15,3% e 1,83 ~ 4,64 mg .100mg CO-1, respectivamente). Através das análises realizadas foi possível identificar diferentes contribuições de fontes assim como diferentes estados de preservação da matéria orgânica sedimentada nos dois sistemas apresentados.

This study aims to characterize the superficial sediments of lakes in black and white waters of an Amazonian floodplain system in terms of carbon content and quality of lignin phenols. "Várzea do Lago Grande Curuái" floodplain is located on the right bank of the Amazon River about 850 km from the estuary. Superficial sediments samples were compared with superficial samples from Lake Caçó, located in Maranhão, the edge of the Amazon ecosystem. Concentration of lignin (λ), Total Organic Carbon (COT), nitrogen and isotope of carbon (δ13C) were undertaken. The results indicate that, in general, the superficial sediments of lakes of white water have low values of COT (1,5 to 3,6%), low concentrations of λ (0,73 to 1,28 mg.100mg CO-1) and high degradation index (0.29 to 2.01). Superficial sediments of lakes of black water had higher values of COT (6,0 to 12,1%) and λ (1,44 to 1,93 mg.100mg CO-1) than the sediments of lakes of white waters, but lower in comparison with the sediments of Caçó Lake. Through such analysis, it was possible to identify different contributions of organic matter sources and the preservation states to the superficial sediments at both sites.

Efeitos das mudanças do uso da terra na biogeoquímica dos corpos d'água da bacia do rio Ji-Paraná, Rondônia / Effects of land use changes in the biogeochemistry of fluvial systems of the Ji-Paraná river basin, Rondônia

Este trabalho discute os efeitos das mudanças do uso do solo na biogequímica dos rios da bacia de drenagem do rio Ji-Paraná (Rondônia). Nesta região, a distribuição espacial do desmatamento e das propriedades do solo resultam em sinais diferentes, possibilitando a divisão dos sistemas fluviais em três grupos: rios com águas pobres em íons e baixo impacto; rios com conteúdo iônico intermediário e impacto médio e rios com elevados conteúdo iônico e impacto antropogênico. As características biogeoquímicas dos rios têm relação significativa com a área de pasto, melhor parâmetro para prever a condutividade elétrica (r² = 0,87) e as concentrações de sódio (r² = 0,75), cloreto (r² = 0,69), potássio (r² = 0,63), fosfato (r² = 0.78), nitrogênio inorgânico (r² = 0.52), carbono inorgânico (r² = 0.81) e carbono orgânico (rain ² = 0.51) dissolvidos. Cálcio e magnésio tiveram sua variância explicada pelas características do solo e pastagem. Nossos resultados indicam que as mudanças observadas na micro-escala constituem "sinais biogeoquímicos" gerados pelo processamento do material nas margens dos rios. A medida em que os rios evoluem para ordens superiores, os sinais persistentes nos canais fluviais estão mais associdados às características da bacia de drenagem (solos e uso da terra). Apesar dos efeitos das mudanças observadas no uso do solo não serem ainda detectáveis na macro-escala (bacia amazônica), a disrupção da estrutura e funcionamento dos ecossistemas é detectável nas micro e meso escalas, com alterações significativas na ciclagem de nutrientes nos ecossistemas fluviais.

Composition of particulate and dissolved organic matter in a disturbed watershed of southeast Brazil (Piracicaba River basin).

The elemental and isotopic composition of particulate and dissolved organic matter was investigated in the Piracicaba River basin, São Paulo State, Brazil. Comparison of riverine organic matter from the Piracicaba River basin, a region where rivers and streams receive urban sewage and industrial effluents, with data reported for the pristine Amazon system revealed significant differences associated with anthropogenic impacts. One important difference was N enrichment in the particulate organic material of the Piracicaba basin rivers, due to (a) urban and industrial effluents, and (b) enhanced phytoplankton growth, which results from the combination of nutrient enrichment and damming of sections of the rivers. Radiocarbon concentrations were overall more depleted (older 14C age) in the Piracicaba basin rivers than in the Amazon, which may reflect the importance of soil erosion in the former. Analyses of stable and radioactive carbon isotopes and lignin-derived compounds indicated that coarse particulate organic material is composed of a mixture of soil particles and degraded organic matter from C3 and C4 vascular plants. Fine particulate organic material was composed mainly of soil particles and phytoplankton cell remains, the latter especially during low water. Ultrafiltered dissolved organic matter was the most degraded fraction according to its lignin oxidation products, and showed the greatest influence of C4 plant sources.