Impact Of Organic Carbon Research Articles

Impact of organic carbon on heavy metals of river sediments and aquatic ecosystems: A review

AbstractOrganic carbon with variable chemical composition sourced primarily from terrestrial and aquatic biogenic input has a significant impact on sediment heavy metal mobility. The present scientific view is unclear in deciphering the role of labile organic carbon in changing sediment heavy metal concentration. The present review critically assesses the impact of various forms of carbon on different geochemically bound heavy metal fractions and their monitoring. It is evident from the review that, the biochemical form of organic carbon (based on degradability and biopolymeric forms), carbon‐geochemical association, and density of organic carbon (light or heavy carbon fractions) plays an important role in determining the bioavailability and toxicity of metals for aquatic organisms. Besides the organic carbon, various sediment conditions that define the behavior of heavy metals include pH, redox condition, sulfide concentration, salinity, temperature, etc. Therefore, it is recommended that carbon relation with heavy metal mobility and stability should be included under long‐term sediment management plans to maintain the sediment quality of the river system.

Impact of organic carbon on sulfide-driven autotrophic denitrification: Insights from isotope fractionation and functional genes

Additional organics are generally supplemented in the sulfide-driven autotrophic denitrification system to accelerate the denitrification rate and reduce sulfate production. In this study, different concentrations of sodium acetate (NaAc) were added to the sulfide-driven autotrophic denitrification reactor, and the S0 accumulation increased from 7.8% to 100% over a 120-day operation period. Batch experiments revealed a threefold increase in total nitrogen (TN) removal rate at an Ac−-C/N ratio of 2.8 compared to a ratio of 0.5. Addition of organic carbon accelerated denitrification rate and nitrite consumption, which shortened the emission time of N2O, but increased the N2O production rate. The lowest N2O emissions were achieved at the Ac−-C/N ratio of 1.3. Stable isotope fractionation is a powerful tool for evaluating different reaction pathways, with the 18ε/15ε values in nitrate reduction ranging from 0.5 to 1.0. This study further confirmed that isotope fractionation can reveal denitrifying nutrient types, with the 18ε (isotopic enrichment factor of oxygen)/15ε (isotopic enrichment factor of nitrogen) value approaching 1.0 for autotrophic denitrification and 0.5 for heterotrophic denitrification. Additionally, the 18ε/15ε values can indicate changes in nitrate reductase. There is a positive correlation between the 18ε/15ε values and the abundance of the functional gene napA, and a negative correlation with the abundance of the gene narG. Moreover, 18ε and 15ε were associated with changes in kinetic parameters during nitrate reduction. In summary, the combination of functional gene analysis and isotope fractionation effectively revealed the complexities of mixotrophic denitrification systems, providing insights for optimizing denitrification processes.

The impact of organic carbon on soot light absorption

The impact of organic carbon (OC) on the light absorption of soot is determined by discrete element modeling coupled with the discrete dipole approximation for computing the scattering of radiation by soot particles. The mass absorption cross-section (MAC) of soot is used widely to determine its light absorption. Typically MAC is obtained from the mass average refractive index of OC and elemental carbon (EC) with large C/H that make up mature soot. As such, MAC can be overestimated by a factor of 3 in fuel-rich flames where newly-formed young soot contains EC with small C/H and OC that predominantly scatters light reducing its absorption by soot. Here a relation for the soot refractive index is derived accounting for soot morphology, maturity and OC content through its band gap at wavelength, λ = 266–1064 nm. Using this relation, the MAC of soot containing OC (up to 50 wt%) is in excellent agreement with carbon black, graphene and soot data. This confirms that soot morphology, maturity and OC content greatly influence light absorption during characterization of in-flame and freshly-emitted soot by laser induced incandescence and light extinction, especially in fuel-rich flames, and need to be properly accounted for in the soot refractive index.

Establishing mainstream nitrite shunt process in membrane aerated biofilm reactors: Impact of organic carbon and biofilm scouring intensity

Establishing one-stage short-cut nitrogen removal processes for carbon captured wastewater has been a challenge. This paper characterizes implementation of a nitrite shunt process in an intermittently aerated membrane aerated biofilm reactor (MABR). The unique characteristics of MABR showed the development of a diverse microbial population facilitating a multi-population coexistence approach to establish the nitrite shunt process. This study also evaluates the impact of soluble COD (sCOD):N ratio and scouring intensity on ammonia and total nitrogen removal efficiencies. Two sCOD:N ratio levels and three scouring modes, including aggressive, normal, and no scouring, were examined in six junior MABR pilots. The pilots were fed chemically enhanced primary treated wastewater with an ammonia concentration of 20 mg/L. The results showed that under intermittent aeration and sCOD:N ratio of 2.5, denitrifiers could out-compete nitrite-oxidizing bacteria (NOB), and a successful nitrite shunt pathway was achieved. However, when wastewater with an sCOD:N ratio of 1.2 was introduced, NOB was the dominant active species. The results also indicated that MABRs with no scouring achieved significantly higher total nitrogen removal, 0.80 g/m 2/d, than the aggressively and normally-scoured MABRs, 0.34 g/m 2 /d, and 0.59 g/m 2/d, respectively. In terms of ammonia removal, the MABRs under normal scouring showed the highest removal of 1.58 g/m 2/d, whereas the MABRs scoured aggressively showed no notable performance either in total nitrogen removal or in ammonia removal. The microbial analysis revealed a higher relative abundance of nitrifiers and denitrifiers in normally-scoured and non-scoured MABRs, respectively.

Numerical Simulation and Sensitivity Analysis for Nitrogen Dynamics Under Sewage Water Irrigation with Organic Carbon

This study is focused on investigating the impacts of organic carbon on the denitrification process of nitrogen transformation and transport. A numerical model, Nitrogen-2D, is modified by considering the impact of organic carbon in the denitrification equation. The modified model is used to simulate the soil nitrogen (including nitrate and ammonium) dynamics under the primary and secondary sewage water irrigation with different organic carbon concentrations. The simulated results of accumulated drainage water amount, soil nitrogen concentration, and nitrogen concentration in the drainage water show that the simulations and measurements are consistent. The comparison of results from the original and improved models shows the necessity to consider the impact of organic carbon. The nitrogen mass balance is calculated to analyze the nitrogen transformation processes quantitatively under different input organic carbon sources. Furthermore, the effect of different input organic carbon sources on the soil nitrogen dynamics is investigated by using the modified Nitrogen-2D model with the calibrated parameters. The input organic carbon source helps to speed up the mineralization and denitrification, which contributes to the slight increase of ammonium concentration and the decrease of nitrate concentration in the shallow soil. Since a large number of soil water and nitrogen transformation and transport parameters are needed when setting up the model, a local sensitivity method is conducted to evaluate the input parameters by the sewage water irrigation case. The results show that the drainage water amount is very sensitive to the exponent n and the coefficient α of the soil water retention function and that the ammonium concentration is very sensitive to the first-order nitrification rate constant, the decomposition rate coefficient in humus pool, and the soil ammonium adsorption coefficient. The nitrate concentration is sensitive to more parameters, especially to the exponent n and the coefficient α in the soil water retention function and to the denitrification rate constant.

Methodological and Environmental Impacts on Bioaccessibility Estimates Provided by Single-Point Tenax Extractions.

Single-point Tenax extractions (SPTEs) of hydrophobic organic contaminants provide estimates of bioaccessibility through consistent measures of the chemical concentration initially in the rapidly desorbing fraction in sediment (C rapT0), such that a constant ratio is expected between SPTE and C rapT0 (C T /C rapT0, where T is the duration of the SPTE). As environmental factors (i.e., aging time and organic carbon content) and contaminant hydrophobicity can affect the C rapT0, the utility of the SPTEs as exposure estimates hinges on the consistency of the C T /C rapT0 ratio. Individually these factors have little impact on the ability of SPTEs to represent bioaccumulation, but the effect of these factors in combination, as well as SPTE methodological variation on the C T /C rapT0 ratio is poorly understood. The current study evaluated how environmental and methodological variation-expressed as varying Tenax to organic carbon mass (Tenax:OC) ratios-impacts the C 24h/C rapT0 ratio of pyrethroids in laboratory-spiked sediments. A multiple regression analysis was used to examine the impact of organic carbon, pyrethroid hydrophobicity, Tenax mass, and aging time on the C 24h/C rapT0 ratio. Only aging time of the pyrethroids in sediment significantly affected the C 24h/C rapT0 ratio with a slight decline of -0.0027/d in the C 24h/C rapT0 ratio, and this decline was considered negligible as a consistent C 24h/C rapT0 ratio of 1.46±0.03 was observed across all experimental treatments. This result further demonstrates the consistency of SPTEs to estimate bioaccessibility of hydrophobic contaminants in sediment and subsequent exposure.

Oxidation of manganese(II) with ferrate: Stoichiometry, kinetics, products and impact of organic carbon

Manganese is a contaminant of concern for many drinking water utilities, and future regulation may be pending. An analysis of soluble manganese (Mn(II)) oxidation by ferrate (Fe(VI)) was executed at the bench-scale, in a laboratory matrix, both with and without the presence of natural organic matter (NOM) and at two different pH values, 6.2 and 7.5. In the matrix without NOM, the oxidation of Mn(II) by Fe(VI) followed a stoichiometry of 2 mol Fe(VI) to 3 mol Mn(II). The presence of NOM did not significantly affect the stoichiometry of the oxidation reaction, indicating relative selectivity of Fe(VI) for Mn(II). The size distribution of resulting particles included significant amounts of nanoparticles. Resulting manganese oxide particles were confirmed to be MnO2 via X-ray photoelectron spectroscopy. The rate of the Mn(II) oxidation reaction was fast relative to typical time scales in drinking water treatment, with an estimated second order rate constant of approximately 1 × 104 M−1 s−1 at pH 9.2 and > 9 × 104 M−1 s−1 at pH 6.2. In general, ferrate is a potential option for Mn(II) oxidation in water treatment.

Impact of organic carbon on hardened properties and durability of limestone cement concrete

In this paper, the effect of organic carbon in ground limestone on the properties and behavior of Portland limestone cement (PLC) concrete in normal and aggressive medium was studied. Three different sources of limestone with total organic carbon of 0.94, 0.48 and 0.18% were considered, the cement replacement ratios were 0, 10, 15, 20 and 25% by weight and water to binder ratio was 0.55.Mechanical properties, XRD and TGA experiments were conducted to evaluate the effect of the previous variables on hardened properties of concrete and hydration process of cement paste. Corrosion rate and polarization resistance of reinforcing PLC concrete specimens immersed in 5.0% sodium chloride solution for 12months were measured using potentiodynamic polarization resistance technique. The sulfate resistance of PLC concrete specimens was also investigated. Concrete specimens exposed to wetting and drying cycles in 5% magnesium sulfate solution for 18months were tested. SEMs of limestone cement paste after magnesium sulfate exposure were performed. The results emphasize the essential role of organic carbon on the properties and behavior of PLC concrete for both normal and aggressive medium especially at high ratios of cement replacement with limestone.

Impact of organic carbon on the leachability of vanadium, manganese, iron and molybdenum from shale residues

From 1942 to the 1966, oil was produced by pyrolysis of shale, in Kvarntorp, Sweden. This generated some 40millionm3 of metal rich pyrolyzed shale and discarded fines that were piled on site with its original metal content almost intact. The present study focuses on the leaching of vanadium, manganese, iron and molybdenum from fines after addition of wood chips and steel slag, in outdoor 1m3 reactor systems at low liquid to solid ratio, in order to evaluate the potential environmental impact and recovery of the elements from the leachates. Seasonal variations were observed, with increased leaching during peak summer. For vanadium and molybdenum, high addition of wood chips decreased the leaching, probably due to adsorption. Manganese showed the opposite behavior while leaching of iron was almost independent of the amount of wood chips. Depending on the systems, up to 2200μgL−1 vanadium, 90μgL−1 molybdenum, 25mgL−1 manganese and 500mgL−1 iron was found in the aqueous phase. Applied to the 40millionm3 pile, the annual leaching of those elements may reach 14ton, 0.6ton, 200ton and 2400ton, respectively.

Impact of organic carbon on weathering and chemical denudation of granular basalt

Bench-scale experiments were conducted to determine rates and patterns of coupled organic matter infusion and weathering in a San Francisco volcanic field (Flagstaff, AZ) basalt sample under experimentally-modeled biotic and abiotic condition and to inform larger-scale collaborative studies at the landscape evolution observatory (LEO), Biosphere 2 (Tucson, AZ), where the same basaltic media is being used in a synthetic hillslope experiment. We postulated that mineral transformations depend significantly on the presence of organic carbon compounds including dissolved natural organic matter (DOM), with organic C simultaneously imprinting the chemical and mineralogical properties of primary and secondary solids undergoing incongruent dissolution. The present work reports on solute releases from Flagstaff basalt (FB) along laboratory-controlled gradients in DOM type and concentration. Loamy sand textured FB was subjected to flow-through, saturated column dissolution experiments using influent solutions with and without DOM compounds. Solutions included Ponderosa pine forest soil O-horizon extracts at three target concentrations: 7, 35, and 70mgL−1C, malic acid (MA) solutions at 7, 35, 70, and 140mgL−1C, and a control without DOM but having comparable inorganic solution composition. Chemical denudation rates for FB dissolution products were calculated from the concentration difference between outflow and inflow solutions. In addition, changes in the composition of the solid phase over the course of the experiment were determined using X-ray diffraction (XRD), X-ray fluorescence (XRF), and selective dissolution (SE). Column experiments supported dissolution rates derived from the literature and indicated a potentially strong effect of plant-derived organic ligands on mineral dissolution congruency and secondary phase precipitation. Both malic acid and DOM enhanced basalt dissolution, with malic acid having larger effect on per unit C basis. The largest relative effect of organic ligands was observed for Fe and Ti. Si/Al and Si/Fe chemical denudation rate ratios indicated non-stoichiometric dissolution, consistent with the observed precipitation of secondary phases, as confirmed by XRD and SE. DOM enhanced precipitation of secondary phases but this effect decreased with increase in amount of DOM added. Stoichiometry of the outflow solutions indicated that basaltic glass was preferentially dissolved in agreement with previous modeling predictions. Results suggest that biotic colonization of FB in the large-scale, long-term LEO experiment is likely to strongly influence the rate and congruency of FB weathering reactions and their distribution across the convergent hillslopes.

Impact of organic carbon and iron bioavailability on the magnetic susceptibility of soils

Microorganisms are known to couple the degradation of hydrocarbons to Fe(III) reduction leading to the dissolution and (trans)formation of Fe minerals including ferro(i)magnetic Fe minerals such as magnetite. The screening of soil magnetic properties, in particular magnetic susceptibility (MS), has the potential to assist in locating and assessing hydrocarbon (e.g. gasoline) contamination in the environment. In order to evaluate this, it must be understood how changes in soil geochemistry and hydrocarbon input impact MS. To this end, we incubated microcosms with soils from six different field sites anoxically and followed the changes in soil MS. In parallel we simulated hydrocarbon (i.e., gasoline) contamination in the same soils under anoxic conditions. We found that in microbially active microcosms both with or without added gasoline, average changes in MS of 6.9±2.6% occurred, whereas in sterile controls the changes were less than 2.5% demonstrating that microbial metabolism played a major role in the (trans)formation of ferro(i)magnetic minerals. The microcosms reached stable MS values after a few weeks to months in four out of the six soils showing an increase in MS while in two soils the MS decreased over time. After stable MS values were reached, further addition of labile organic carbon (i.e., lactate/acetate) did not lead to further changes in MS, but the addition of Fe(III) oxyhydroxides (ferrihydrite) led to increases in MS suggesting that the changes in MS were limited by bioavailable Fe and not by bioavailable organic carbon. In the control experiments without carbon amendment, we observed that natural organic matter was mobilized from the soil matrix by water or microbial growth medium (0.33-0.47mL/g field moist soil) added to the microcosms, and that this mobilized organic matter also stimulated microbial Fe metabolism and thus also led to a microbially driven change in MS. This study shows that changes in MS after an increase of the amount of bioavailable organic carbon can occur in a variety of soils. It also suggests that whether MS increases or decreases depends on the initial MS of the soil and the extent of the MS change seems to depend upon the amount of bioavailable Fe(III).

Impact of organic carbon and nutrients mobilized during chemical oxidation on subsequent bioremediation of a diesel-contaminated soil

Remediation with in situ chemical oxidation (ISCO) impacts soil organic matter (SOM) and the microbial community, with deleterious effects on the latter being a major hurdle to coupling ISCO with in situ bioremediation (ISB). We investigate treatment of a diesel-contaminated soil with Fenton’s reagent and modified Fenton’s reagent coupled with a subsequent bioremediation phase of 187d, both with and without nutrient amendment. Chemical oxidation mobilized SOM into the liquid phase, producing dissolved organic carbon (DOC) concentrations 8–16 times higher than the untreated field sample. Higher aqueous concentrations of nitrogen and phosphorous species were also observed following oxidation; NH4+ increased 14–172 times. During the bioremediation phase, dissolved carbon and nutrient species were utilized for microbial growth-yielding DOC concentrations similar to field sample levels within 56d of incubation. In the absence of nutrient amendment, the highest microbial respiration rates were correlated with higher availability of nitrogen and phosphorus species mobilized by oxidation. Significant diesel degradation was only observed following nutrient amendment, implying that nutrients mobilized by chemical oxidation can increase microbial activity but are insufficient for bioremediation. While all bioremediation occurred in the first 28d of incubation in the biotic control microcosm with nutrient amendment, biodegradation continued throughout 187d of incubation following chemical oxidation, suggesting that chemical treatment also affects the desorption of organic contaminants from SOM. Overall, results indicate that biodegradation of DOC, as an alternative substrate to diesel, and biological utilization of mobilized nutrients have implications for the success of coupled ISCO and ISB treatments.

Impact of Organic Carbon on the Biodegradation of Estrone in Mixed Culture Systems

The effects of organic carbon concentrations and loading on the degradation of estrone (E1) were examined under various conditions in batch reactors and membrane-coupled bioreactors (MBRs). Experiments examined effects on individual microorganisms (substrate competition and growth) and on the whole community (selection). Substrate competition with organic carbon (competitive inhibition and catabolic repression) was not a factor in E1 degradation (P = 0.19 and 0.29 for two different analyses). Conversely, addition of organic carbon increased E1 degradation rates, attributable to biomass growth in feast-famine reactors over a five-day period (P = 0.016). Subsequently, however, community dynamics controlled E1 degradation rates, with other organisms outcompeting E1 degraders. More moderate but sustained increases in E1 degradation rates were observed under starvation conditions. Low influent organic carbon strength was detrimental to E1 degradation in MBRs, where organic carbon concentration and loading were decoupled (P = 0.018). These results point to the importance of multiple substrate utilizers in E1 degradation. They also suggest that while initial growth of biomass depends on the presence of sufficient organic carbon, further enrichment under starvation conditions may improve E1 degradation capability via the growth and/or stimulation of multiple substrate utilizers rather than heterotrophs characterized by an r-strategist growth regime.

Impact of Organic Carbon on the Stability and Toxicity of Fresh and Stored Silver Nanoparticles

Studies investigating the impact of particle size and capping agents on nanosilver toxicity in pristine laboratory conditions are becoming available. However, the relative importance of known environmental mitigating factors for dissolved silver remains poorly characterized for nanosilver in context with existing predictive toxicity models. This study investigated the implications of freshly prepared versus stored 20 and 100 nm nanosilver stocks to freshwater zooplankton (Ceriodaphnia dubia) in presence and absence of dissolved organic carbon (DOC). Results indicated that while the acute toxicity of nanosilver decreased significantly with larger size and higher DOC, storage resulted in significant increases in toxicity and ion release. The most dramatic decrease in toxicity due to DOC was observed for the 20 nm particle (2.5-6.7 fold decrease), with more modest toxicity reductions observed for the 100 nm particle (2.0-2.4 fold) and dissolved silver (2.7-3.1 fold). While a surface area dosimetry presented an improvement over mass when DOC was absent, the presence of DOC confounded its efficacy. The fraction of dissolved silver in the nanosilver suspensions was most predictive of acute toxicity regardless of system complexity. Biotic Ligand Model (BLM) predictions based on the dissolved fraction in nanosilver suspensions were comparable to observed toxicity.

The impact of organic carbon on the performance of a high rate nitrifying trickling filter designed to pre-treat potable water

The application of nitrifying trickling filters (NTFs) to potable water treatment is less well understood than their application to wastewater treatment, particularly regarding the effect of low ammonia substrate concentrations and organic carbon loading on filter performance. A large pilot-scale NTF was operated under conditions that simulated the raw water quality of poorly protected catchments typically found in SE Asia, with the objective of reducing the ammonia driven chlorine demand during disinfection. The efficacy of a high rate NTF to remove low concentrations of ammonia (0.5-5.0 mg NH(4)-N L(-1)) in the presence of high organic carbon (1-12 mg soluble biochemical oxygen demand (sBOD(5)) L(-1)) was investigated. Results demonstrated that 90 to 100% of nitrification was maintained only when the carbon load was less than 0.7 g sBOD(5) m(-2) d(-1) (<4 mg sBOD(5) L(-1)). Once the organic load was increased beyond 0.75 to 2.1 g sBOD(5) m(-2) d(-1) (4.5-12.1 mg sBOD(5) L(-1)), a linear decline in nitrification from 70 to 15% was observed within a timeframe of 8 to 10 d. The impact of high organic loads on the distribution of nitrification down the NTF was also investigated. Results confirmed that carbon loads greater than 0.95 g sBOD(5) m(-2) d(-1) (>5.5 mg sBOD(5) L(-1)), severely suppressed nitrification throughout the entire filter bed.

Impact of organic carbon on nitrification performance of different biofilters

Nitrification rate as a function of total ammonia nitrogen (TAN) concentration, with and without the interaction of organic matter, was investigated for three types of biofilters of laboratory scale: floating bead filter, fluidized sand filter, and submerged bio-cube filter. The performance of each type of biofilter was evaluated using a 5-reactor series with synthetic solutions containing different carbon/nitrogen ratios (C/N=0, 0.5, and 2.0). The tests were run at representative cool water aquaculture system temperatures of 15 and 20°C. The experimental results showed, within the lower total ammonia concentration range, a first-order nitrification rate with a highly linear regression for all three types of biofilters without the interaction of organic carbon at both test temperatures. However, with the addition of organic carbon, the nitrification rate of all three types of biofilters decreased exponentially. The reduction of nitrification rates of the biofilters was about 60–70% for a substrate concentration of 10mgTANl−1 when the COD/N ratio increased from 0 to 3. The temperature impact on biofilter nitrification rate was not significant under the two temperatures tested. The results of this study provide useful information for nitrification biofilter design of cool and cold water applications.

Precambrian sedimentary carbonates: carbon and oxygen isotope geochemistry and implications for the terrestrial oxygen budget

Abstract Carbon isotope values of 260 Precambrian limestones and dolomites (most of them being substantially unaltered) have yielded an overall mean of δ 13 C = +0.4 ± 2.7‰ vs. PDB; the corresponding oxygen values average at δ 13 O = +20.0 ± 4.2‰ vs. SMOW. Like the overall mean, the δ 13C values furnished by individual carbonate occurrences are, as a rule, fairly “modern” and almost constant as from the very beginning of the sedimentary record. A remarkable exception are the “heavy” dolomites of the Middle Precambrian Lomagundi Group, Rhodesia, with δ 13 C = +9.4 ± 2.0‰ vs. PDB. As a result of our measurements, the sporadic occurrence in the geological past of anomalously heavy carbonates seems to be established. The approximate constancy around zero per mill of the δ 13C values of marine carbonates through geologic time would imply a corresponding constancy of the relative proportion of organic carbon in the total sedimentary carbon reservoir since about 3.3 · 109 y ago (with Corg/Ctotal ≅ 0.2). Utilizing this ratio and current models for the accumulation of the sedimentary mass as a function of time, we get a reasonable approximation for the absolute quantity of organic carbon buried in sediments and, accordingly, of photosynthetic oxygen released. Within the constraints of our model (based on a terrestrial degassing constant λ = 1.16 · 10−9 y−1) close to 80% of the amount of oxygen contained in the present oxygen budget should have been released prior to 3 · 109 y ago. Since geological evidence indicates an O2-deficient environment during the Early and most parts of the Middle Precambrian, there is reason to believe that the distribution of this oxygen between the “bound” and the “molecular” reservoir was different from that of today (with effective O2-consuming reactions bringing about an instantaneous transfer to the crust of any molecular oxygen released). Accordingly, the amount of Corg in the ancient sedimentary reservoir as derived from our isotope data is just a measure of the gross amount of photosynthetic oxygen produced, withholding any information as to how this oxygen was partitioned between the principal geochemical reservoirs. As a whole, the carbon isotope data accrued provide evidence of an extremely early origin of life on Earth since the impact of organic carbon on the geochemical carbon cycle can be traced back to almost 3.5 · 109y.