Origin of B in of pore fluids at cold seep sites on the Oomine Ridge
At cold seep sites on the Oomine Ridge, the B concentration in the pore fluids increased with depth (Figure 2). Possible sources of B are organic matter desorption, which occurs at relatively low temperatures (You et al. [1993b]; Brumsack et al. [1992]), and smectite-illite alteration, which occurs between 50°C and 160°C (You et al. [1996]). Organic matter desorption is related to organic matter decomposition and thus results in well-correlated B and NH4+ concentrations with ΔB/ΔNH4+ ratios of 0.1 mol/mol (Teichert et al. [2005]). In this study, ΔB/ΔNH4+ was about 4 mol/mol at the cold seep sites on the Oomine Ridge; thus, the ratio demonstrated B enrichment by a factor of 40 compared with the expected ratio for organic matter desorption (Figure 3). This excess B suggests that B derived from smectite-illite alteration occurring in a higher-temperature environment is supplied to the pore fluids in the surface sediments at these cold seep sites and that the supplied fluids were subjected to temperatures between 50°C and 160°C.
At Site C0001, near the surface trace of a megasplay fault in analogy with the Oomine Ridge, the coring was operated up to 458 m bsf during Integrated Ocean Drilling Program (IODP) Expedition 315 (Expedition 315 Scientists [2009a]). The results indicated that the heat flow was 47 mW/m2 and that there was no B enrichment. On the contrary, at Site C0002 on the northern rim of Kumano Basin (Expedition 315 Scientists [2009b]), the maximum depth reached during the Expedition 315 drilling was 1,057 m bsf. In addition, the heat flow was 56 mW/m2 (Harris et al. [2011]) and there was no B enrichment. These heat flow data indicate that the high-temperature zone in which clay mineral dehydration (CMD) can occur was not reached by drilling in Kumano Basin. Thus, the lack of B enrichment at both sites implies that B-rich fluids at either depth did not pass through the hanging wall of the megasplay (C0001) or Kumano Basin (C0002). This result leads to the question of how B-rich fluids can flow to the Oomine Ridge.
In Nankai Trough off Muroto, high B concentrations in pore fluids up to 3 mmol/kg are shown in the décollement zone, which is attributed to fluid flow in the décollement zone (You et al. [1993a]). In the Japan Trench forearc, B shows an increase in pore fluids, which is also attributed to fluid advection in sediments (Deyhle and Kopf [2002]). In all cases, lower chlorides than that of SW were noted. Thus, inputs of B by fluid flow seem to be clear in these areas. In the Nankai forearc off Kumano, fluids may flow through the megasplay fault, although we were unable to detect corresponding B enrichment at Site C0004 penetrating the megasplay fault (Expedition 316 Scientists [2009a]). Very few cold seep sites have been observed near the surface trace of the megasplay fault near Site C0004 (Ashi et al. [2009b]). These observations suggest that the megasplay near Site C0004 is not an active pathway for reductive fluids. A possible explanation for the different character of the megasplay between Oomine and C0004 is the difference in tectonic and hydrologic activities along the strike of the megasplay fault (e.g., Kimura et al. [2011]).
Isotopic compositions of pore fluids at cold seep sites on the Oomine Ridge
At the cold seep sites on the Oomine Ridge, the observed δ18OH2O and δDH2O were negative (Figure 2), which led Toki et al. ([2004]) to conclude that these fluids originated from groundwater. As suggested in ‘Origin of B in of pore fluids at cold seep sites on the Oomine Ridge’ section, however, if the fluids were derived from CMD, the values of δ18OH2O and δDH2O would be positive and negative, respectively (Magaritz and Gat [1981]). It is possible that during their ascent to the seafloor, fluids derived from CMD mixed with fluids in sediments shallower than the estimated depth range of 1.5 to 3.5 km bsf, where temperatures from 50°C to 160°C enable CMD to occur. Such chemical and isotopic features have been reported in the Barbados subduction zone, although the distribution of δDH2O has not been explained by any possible processes in the sediments (Vrolijk et al. [1990], [1991]).
The chemical and isotopic compositions of the Oomine Ridge cold seep pore fluids also reflect the mixing of low Cl−, δ18O, and δD fluids with SW (Figure 2). The data for Cl− and δ18O, however, are scattered (Figure 2), implying that the pore fluids did not result from the simple mixing of two sources such as SW and another end member. Among the cold seep samples, sample D949 C3-3 (Cl− = 498 mmol/kg, B = 1.3 mmol/kg, δ18OH2O = −0.4‰, δDH2O = −3.4‰) differs most from SW with respect to these values (Figure 2). If the data of D949 C3-3 can be explained by some end members, the other data also can be explained by those end members with different mixing ratios. Therefore, we examined various possible sources in which the mixing with freshwater derived from CMD might explain the chemical and isotopic compositions of the pore fluids in the cold seeps on the Oomine Ridge.
Possible sources of fluids in cold seeps on the Oomine Ridge
Seawater
First, we calculated the chemical and isotopic compositions of the SW samples from D949 (C1-0 and C3-0) and D1062 (C2-0, C3-0, C4-0, and C5-0), which consisted of SW overlying the sediment in each corer collected just before the sediments were sampled (Table 3). The chemical and isotopic compositions in these samples were averaged as Cl− = 547 ± 8 mmol/kg, B = 0.416 ± 0.015 mmol/kg, δ18OH2O = −0.09 ± 0.21‰, and δDH2O = +1.1 ± 1.0‰. All of these values fall within the range of those of North Pacific deep SW (Reid [2009]); therefore, we adopted these values for the chemical and isotopic compositions of SW in this study.
Freshwater derived from CMD
The chemical and isotopic compositions of freshwater derived from CMD (δ18OCMD and δDCMD) depend on those of the clay minerals (δ18Oclay and δDclay) and the equilibrium temperature T (K) of the reaction. The isotopic fractionation between clay minerals and ambient pore fluids for δ18O (Sheppard and Gilg [1996]) and δD (Capuano [1992]) is expressed as a function of the reaction temperature:
(1)
(2)
In these equations, we considered δ18Oclay to range from +17‰ to +26‰ and δDclay to range from −95‰ to +33‰ because these are the reported value ranges for clay minerals in marine sediments (Savin and Epstein [1970]; Yeh [1980]; Capuano [1992]). Then, using Equations 1 and 2, we calculated δ18OCMD to range between −3‰ and +17‰ and δDCMD to range between −85‰ and +79‰ for a temperature range of 50°C to 160°C. The B concentration of freshwater derived from CMD is unknown; therefore, we used the value of the Kumano mud volcanoes near the study area (23 ± 8 mmol/kg) as the reference value (Toki et al. [2013]). Since the value of 23 mmol/kg is taken from the mud volcano site, the accuracy should be lower, and the error would be larger than 8 mmol/kg. But this value is essential to the modeling, and it should be stated for the fairness.
Shallow pore fluids in Nankai accretionary prism sediment
From 2007 to 2008, during IODP Expeditions 315 and 316, D/V Chikyu drilled into the slope of the Nankai accretionary prism to a depth of up to 1,052 m bsf and recovered pore fluids from the sediments (Figure 1b) (Ashi et al. [2009a]; Screaton et al. [2009]). Pore fluid δ18OH2O and δDH2O values at Sites C0001 and C0002, drilled during Expedition 315, have been reported (Expedition 315 Scientists [2009b]), although at Sites C0004 and C0008, drilled during Expedition 316, only pore fluid δ18OH2O has been reported (Expedition 316 Scientists [2009a], [b]). The δ18OH2O and δDH2O at all four sites, however, have been measured by Dr. H. Tomaru using the method described by Expedition 315 Scientists ([2009a]). Dr. Tomaru distributed the data to all researchers associated with the drilling expeditions, including onshore researchers requesting the data. We therefore used these data to construct vertical profiles of δ18OH2O and δDH2O (Figure 4). At depths deeper than 200 m bsf at all sites drilled during Expeditions 315 and 316, δ18OH2O and δDH2O were nearly constant: δ18OH2O varied between −4.5‰ and −2‰, and δDH2O varied between −15‰ and −10‰ (Figure 4). On the contrary, at depths shallower than 200 m bsf at all sites, these values gradually became close to that of SW. These gradients suggest that a fluid source with constant δ18OH2O and δDH2O below 200 m bsf would mix with SW above 200 m bsf. In such cases, the fluid source below 200 m bsf would be recognized as an end member in the shallow sediments of the Nankai accretionary prism slope (below 200 m bsf and above 1.5 to 3.5 km bsf). In this study, we refer to the fluids in the sediments of the Nankai accretionary prism slope below 200 m bsf and above 1.5 to 3.5 km bsf as shallow pore fluids (SPF). The SPF ubiquitous in the sediments of the Nankai accretionary prism slope would be mixed with deep-sourced fluids derived from CMD before seeping at the cold seep sites on the Oomine Ridge. In our subsequent discussion, we use the following chemical and isotopic compositions of SPF from Site C0001 on the outer ridge of the Nankai accretionary prism as SPF values: Cl− = 549 ± 4 mmol/kg, B = 0.217 ± 0.057 mmol/kg, δ18O = −2.5 ± 0.4‰, and δD = −10.0 ± 2.8‰ (Expedition 315 Scientists [2009a]).
Freshwater from methane hydrate dissociation
A final factor that can influence the chemical and isotopic compositions of the pore fluids is the freshwater derived from MH dissociation. MH has never actually been recovered from Site C0001, which is situated in a position similar to the Oomine Ridge (Ashi et al. [2009a]). However, discontinuous bottom-simulating reflectors (BSRs) suggesting the presence of MH have been observed beneath the slope of the Nankai accretionary prism (e.g., Colwell et al. [2004]). Moreover, MH was recovered from several hundred meters below the seafloor at Site C0008, which is near the surface trace of another megasplay fault on the seaward side of the Oomine Ridge (Screaton et al. [2009]). In general, MH is recovered where sand layers occur (Ginsburg et al. [2000]), although beneath the Nankai accretionary prism slope, which is composed mainly of silty clay, dispersed MH may be present (Screaton et al. [2009]). Taken together, these findings suggest that it is possible for freshwater derived from MH dissociation to contribute to the fluids supplied to the cold seeps on the Oomine Ridge. Therefore, we also considered freshwater from MH dissociation in our estimation of possible contributions to the seepage fluid.
When MH forms in sediments, it consists mainly of CH4 and water, excluding salt from the ambient SW (e.g., Sloan and Koh [2008]). When MH is recovered during drilling, the MH dissociates, depending on the temperature and pressure conditions, to release CH4 and water (Hesse and Harrison [1981]; Ussler and Paull [1995]). In vertical profiles of pore fluids, samples influenced by MH dissociation are characterized by a negative Cl− concentration spike and positive δ18OH2O and δDH2O values (Kvenvolden and Kastner [1990]). Experimentally determined δ18OH2O and δDH2O fractionation factors during MH formation show a shift to heavier values from ambient water to the formation water; that is, Δδ18O shifts from +2.8‰ to +3.2‰ and ΔδD shifts from +16‰ to +20‰ (Maekawa [2004]; Maekawa and Imai [2000]). Here, we adopt as the reference value Δδ18O = +3.1‰, which was obtained in the Nankai Trough gas hydrate area (Tomaru et al. [2004]).
If MH has formed in the vicinity of the outer ridge, then, given the composition of the SPF at Site C0001 (Cl− = 549 ± 4 mmol/kg, δ18OH2O = −2.5 ± 0.4‰, and δDH2O = −10.0 ± 2.8‰) and the experimentally determined isotope fractionation values of Δδ18O = +3.1‰ and ΔδD = +16‰ to +20‰, the isotopic composition of the formation water of MH can be estimated to be δ18OH2O = +0.6 ± 0.4‰ and δDH2O = +6.0 ± 2.8‰ to +10.0 ± 2.8‰. We used these values to calculate the contribution of MH dissociation to the pore fluids on the Oomine Ridge.
Mixing model for the formation of fluids supplied to the Oomine Ridge cold seeps
We used a mixing model to explain the compositions of pore fluid at the Oomine Ridge cold seeps. Using the end-member values listed in Table 4, we solved the following equations:
(3)
(4)
(5)
(6)
where each source is denoted by a subscript previously defined. X, Y, Z, and W denote the mixing ratios of SW, CMD, SPF, and MH dissociation, respectively. The calculation outline is schematically drawn in Figure 5. Assuming the feasible combination of δ18OCMD and δDCMD given by Equations 1 and 2 for 50°C to 160°C as the reaction temperature of CMD, we calculated the mixing ratios where the Oomine seep values lie on the same plane as that of the combination of SW, CMD, SPF, and MH values. For obtained mixing ratios, we verified the existence of a solution in which the predicted B concentration coincides with the observed B concentration; thus, we can accept the results. At first, we considered three-end-member mixing model. One of four mixing ratios (X-W) is forced to zero, and all Equations 3, 4, 5, 6, and 7 are used to statistically obtain the other three ratios. Although several attempts were made by normalizing the coefficients to the same magnitude, all four cases resulted in prediction error much larger than 10%. Thus, neglecting any factor of the four ratios was rejected.
When we consider a mixing model with four components (end members) including SW, freshwater derived from CMD, SPF, and freshwater derived from MH dissociation, several solutions are possible. For example, for an equilibrium temperature of 160°C, we obtained the solution (X, Y, Z, W) = (0.47, 0.044, 0.44, 0.047) and (δ18OCMD, δDCMD) = (+16.5‰, +3‰); for an equilibrium temperature of 110°C, we obtained (X, Y, Z, W) = (0.70, 0.042, 0.21, 0.048) and (δ18OCMD, δDCMD) = (+3.7‰, −59‰). Using other clay mineral compositions and equilibrium temperatures, other solutions are possible. In particular, for (δ18Oclay, δDclay) = (+26‰, −95‰) and for an equilibrium temperature of 50°C, we obtained (X, Y, Z, W) = (0.67, 0.042, 0.24, 0.048) and (δ18OCMD, δDCMD) = (+5.6‰, −50‰). These results indicate that although it is not possible with this model to constrain the equilibrium temperature, the four-end-member model can nevertheless explain the seepage fluid compositions. We conclude that both MH dissociation and SPF contribute to the pore fluids in the cold seeps on the Oomine Ridge. The results indicate that the contributions of SW and SPF, SW > 40% and SPF = 20% to 50%, are dominant, followed by freshwater from clay minerals, CMD = approximately 4%, and MH dissociation, MH = approximately 5%, which contributes the least. The most important finding is that pore fluids at cold seep sites on the Oomine Ridge cannot be explained without considering CMD, SPF, and MH dissociation.
Behavior of pore fluids in sediments off Kumano
At the seepage sites on the Oomine Ridge, the observed B concentrations were greater than could be explained by organic matter degradation, suggesting that the seeps at the site are supplied with fluids derived from CMD at 50°C to 160°C Toki et al. ([2013]) have shown that Li as well as B is supplied to the Kumano mud volcanoes and that the presence of Li can be attributed to the fluids passing through layers with temperatures of 150°C to 160°C before reaching the seepage sites. The isotopic compositions of the pore fluids of the mud volcanoes also indicate derivation from CMD (Toki et al. [2013]). Thus, the mud volcano fluids ascend from about 4 km bsf (Figure 6; Source A). Moreover, these deep-origin fluids are not overprinted by other fluids in the shallow sediments during their ascent. This scenario can explain the concentrations of other components derived from great depth, including B and Li. The sediment thickness in Kumano Basin is only about 2 km (Expedition 315 Scientists [2009b]); therefore, the rock around Source A at 4 km bsf is likely composed of old accretionary sediments in the lower part of the accretionary prism (Figure 6).
The results obtained in this study suggest that the pore fluid composition at the seepage sites on the Oomine Ridge reflects contributions from other sources, in addition to freshwater from CMD. Therefore, as the source fluids ascend from depth below the seafloor, they likely mix with pore fluids in the shallower layers of the accretionary prism before finally seeping out at the seafloor. However, when we considered the contributions only from SPF in the shallow accretionary prism, which is represented by fluids obtained during deep drilling, freshwater derived from CMD, and SW, the resulting contribution ratios could not explain the observed B concentration (‘Shallow pore fluids in Nankai accretionary prism sediment’ section). When we also considered a contribution of fluids derived from MH dissociation, we obtained the following contribution ratios in the seepage fluid (‘Freshwater derived from CMD’ section): about 4% fluid derived from CMD, about 5% fluid derived from MH dissociation, 20% to 50% SPF of the accretionary prism, and more than 40% SW (Figure 6; Source B). These ratios can explain the observed chemical and isotopic compositions of the pore fluids at the cold seep sites on the Oomine Ridge. Therefore, we conclude that fluids from MH dissociation, CMD, and SPF likely contribute to the pore fluids of the cold seeps.
The results of our estimation of fluid sources suggest that the mode of transport differs between the Oomine Ridge and the Kumano mud volcanoes. In the case of the Kumano mud volcanoes, both source fluids in sediments and the sediments themselves ascend to the seafloor, whereas on the Oomine Ridge, the source fluids mix with SPF sediments and with fluid from MH dissociation as they ascend to the seafloor, although the sediments themselves do not ascend. These different modes of fluid transport are consistent with hydrocarbon distribution differences between the Kumano mud volcanoes and the Oomine Ridge. Hydrocarbons of thermogenic origin are found only in the Kumano mud volcanoes, even though the fluids supplied to both the seepage sites on the Oomine Ridge and the Kumano mud volcanoes originate in environments with temperatures of more than 50°C (Toki et al. [2013]). CH4 of microbial origin is distributed ubiquitously in the shallow sediments above several hundred meters below the seafloor in the accretionary prism off Kumano (Toki et al. [2012]). Thus, sediments containing hydrocarbons of thermogenic origin rise to the seafloor within the Kumano mud volcanoes and are observed in the pore fluids in the subsurface sediments. In contrast, the fluids supplied to the Oomine Ridge contain CH4 of microbial origin from the shallow sediments through which the fluids passed during their ascent to the seafloor.
On the basis of the correlation between decreases in the isotopic compositions of the pore fluids and Cl− concentration, Toki et al. ([2004]) inferred that the source of the seepage fluids on the Oomine Ridge is laterally transported meteoric water. The drilling beneath the seafloor since 2007 has revealed chemical and isotopic compositions of the pore water in the sediments to several hundred meters below the seafloor. The isotopic compositions of the pore water in the shallow sediments of Nankai accretionary prism both had negative values, similar to those of meteoric water (Figure 2). In this study, we focused on B concentrations in the pore fluids, which showed that the seepage fluids on the Oomine Ridge as well as Kumano mud volcano fluids are influenced by freshwater derived from CMD. The source fluids of the cold seeps can thus become mixed with SPF during their ascent to the seafloor. We observed no Li anomaly on the Oomine Ridge; thus, the source fluids did not pass through environments with temperatures above 150°C. We cannot rule out the possibility, however, that the characteristics of the original fluids in the deeper environments have been changed by mixing with SPF in the shallower sediments during the ascent. In the future, by conducting experiments with water and rock to determine trace elements not analyzed by You et al. ([1996]), a tracer that sensitively records information from deeper environments should be identified and utilized.