3.1. Isotopes and spatial temperature responce to groundwater discharge in mixing zone
The saltwater wedge is a mix of seawater and freshwater with salinity of about 25 psu (Fig. 2) and is annually observed in the winter season in the Razdolnaya R. estuary (Zvalinsky et al. 2010). The topographic depression (stations 6–11, Fig. 2) is separated from the sea by a bar and shallow liman lake about 5 km long that prevents penetration of the seawater with salinity of 34 psu even during syzygial tides.
An extreme value of all three radium isotopes is registered in the deepest-water cross-section at Station 6 and their overall increased activity rate is registered along the topographic depression at Stations 5–11 (Table 1). This extreme value is due to a fivefold decrease in the activity of 224Ra isotopes at stations 5 to 11. However, the activity of 223Ra isotopes decreased by less than two times. From this, it follows that the period of advective water exchange in this part of the mixing zone is less than the half-life of 223Ra radionuclides. However, this period exceeds the half-life of 224Ra radionuclides (3.66 days). No such variation can be traced in the activity value of 228Ra isotopes, excluding st. 6, which is not a surprise since the time spent by waters in the estuary is significantly less than the half-life of these radionuclides (half-life is 5.6 years). The names of water types are as follows: RW — river water, GWD —groundwater discharge, SW — seawater, HTBW — high-turbidity brackish water (mixture of RW and SW), and are presented based on the activity of isotopes Ra in end-members water (Table 1).
Table 1 Depth (m), salinity (S), activities radium isotopes (dpm 100L−1) in bottom layer of the estuary. RW: river water, GWD: groundwater discharge, TGW: transformed groundwater, SW: seawater, HTBW: high-turbidity brackish water (mixture of RW and SW).
St. № / water mass
|
Depth
|
S
|
ex223Ra
|
ex224Ra
|
223Ra/224Ra
|
228Ra
|
228Ra/224Ra
|
1 / RW
|
2.3
|
0.14
|
0.14 ± 0.01
|
9.81 ± 0.15
|
0.014
|
5.37 ± 0.03
|
0.5
|
2 / RW
|
1.6
|
0.14
|
0.04 ± 0.02
|
5.64 ± 0.30
|
0.007
|
13.75 ± 0.05
|
2.4
|
3 / RW
|
3.7
|
0.13
|
0.19 ±0.11
|
1.68 ± 0.24
|
0.113
|
10.07 ± 0.08
|
6.0
|
4 / RW
|
2.5
|
0.2
|
0.28 ± 0.10
|
1.8 ± 0.13
|
0.156
|
12.26 ± 0.14
|
6.8
|
5 / GWD
|
3.5
|
21.66
|
1.41 ± 0.11
|
47.01 ± 0.15
|
0.030
|
84.91 ± 0.14
|
1.8
|
6 / GWD
|
7.9
|
25.19
|
2.85 ± 0.17
|
66.32 ± 0.60
|
0.043
|
159.15 ± 0.13
|
2.4
|
7 / GWD
|
7.5
|
25.23
|
1.85 ± 0.12
|
48.43 ± 0.69
|
0.038
|
70.69 ± 0.14
|
1.5
|
8 / GWD
|
6.9
|
25.37
|
1.94 ± 0.17
|
30.02 ± 0.60
|
0.065
|
92.21 ± 0.12
|
3.1
|
9 / GWD
|
6.6
|
25.19
|
1.09 ± 0.08
|
26.57 ± 0.33
|
0.041
|
79.49 ± 0.15
|
3.0
|
10 / GWD
|
6.3
|
24.95
|
1.06 ± 0.07
|
19.29 ± 0.32
|
0.055
|
43.52 ± 0.15
|
2.3
|
11 / GWD
|
4.3
|
25.4
|
1.53 ± 0.13
|
13.3 ± 0.30
|
0.115
|
59.55 ± 0.14
|
4.5
|
12 / HTBW
|
1.3
|
10.49
|
0.77 ± 0.09
|
22.73 ± 0.25
|
0.034
|
39.63 ± 0.15
|
1.7
|
13 / HTBW
|
0.6
|
16.63
|
1.45 ± 0.14
|
30.6 ± 0.43
|
0.047
|
49.91 ± 0.12
|
1.6
|
14 / SW
|
3.8
|
32.34
|
0.29 ± 0.10
|
9.96 ± 0.49
|
0.029
|
24.82 ± 0.11
|
2.5
|
15 / SW
|
7.7
|
34.07
|
0.02 ± 0.05
|
0.9 ± 0.49
|
0.022
|
19.79 ± 0.16
|
22.0
|
16 / SW
|
15.2
|
34.32
|
0.08 ± 0.05
|
3.82 ± 0.24
|
0.021
|
29.67 ± 0.14
|
7.8
|
17 / SW
|
16.8
|
34.36
|
0.58 ± 0.05
|
12.39 ± 0.36
|
0.047
|
29.96 ± 0.16
|
2.4
|
As seen in Fig. 3, the highest total activity rate of radium isotopes 224Ra, 223Ra and 228Ra is observed at Station 6 and an increased activity rate is observed all across the topographic depression with its saltwater wedge. The discharge of groundwater in the deepest section of the estuary creates an increased radium activity rate and a positive temperature anomaly for 15 km (Fig. 3b). This is explained by the fact that, with distance from the estuary bar, groundwater temperatures rise from below-zero values in the sea to +4°C within the estuary floodplain (see the section on objects and methods).
3.2. Oxygen response to groundwater discharge
A negative correlation between the three radium isotopes and oxygen saturation exists in the estuary’s near-bottom waters in winter (Fig. 4). Groundwater normally has a low level of DO and, when it discharges to the shelf, there is a negative correlation between radium radionuclides and the oxygen saturation of water (McCoy et al. 2011; Peterson et al. 2016; Guo et al. 2020).
The negative correlation of oxygen saturation is best of all seen for short-lived isotopes 224Ra (Fig. 4). That is why we use the activity rate of 224Ra relative to salinity (Fig. 5a) to show that each body of water also has an DO signature (Fig. 5b). The drop of oxygen saturation of the near-bottom waters to 67% corresponded to the waters with a maximum activity rate of excess isotopes 224Ra, and, generally, the near-bottom waters in groundwater discharge zone with virtually invariable salinity at Stations 5–11 were under-saturated with DO. At the same time, water is oversaturated with oxygen up to 150% at salinity more than 30 psu beyond the estuary bar (Fig. 5). The decrease of oxygen saturation to 35% in the vicinity of Station 5 with a relatively small depth of 3.5 m is explained by over-splash of oxygen-low waters from the downstream reach as there are reversing currents in this area.
In the warm season, the saltwater wedge in the Razdolnaya River Estuary has an DO close to zero due to the intensification of production-destruction processes as well as to the high water turbidity and, accordingly, low photosynthetically active radiation of the near-bottom water layer (Tishchenko et al. 2017). However, suspended matter concentrations are relatively low in winter and, the photic zone normally extends to the bottom everywhere, with nutrients concentrations being very high (Zvalinsky et al. 2010). That is why photosynthesis prevails over organic matter destruction and oxygen oversaturation is observed in the Razdolnaya River Estuary in winter. Not excepting that the key factor of DO-specific conditions for the Razdolnaya River Estuary is the balance of organic matter production-destruction (Zvalinsky et al. 2010), results in Fig. 5 are indicative of groundwater discharge influence on formation of DO-specific conditions of the water area.
3.3. Synoptically temperature variability as a response to the groundwater discharge and scenario of the formation DO regime in the estuary
The data indicate that a temperature anomaly is formed in the area of groundwater discharge influence (Fig. 3b), i.e., the bottom water temperature makes it possible to track groundwater discharge intensity indirectly over time. The bottom water temperature variation which took place at station 9 (Fig. 1) between 27 January 2014 and 11 March 2014 indicates that the groundwater discharge increased during the entire freeze-up period (Fig. 6). Clear extreme values can be observed against the background of a general increase in water temperature in the bottom layer of the estuary at roughly 2-week intervals (Fig. 6). These extremums coincide with the two-week tidal cycle (http://esimo.oceanography.ru/tides/). Irregular daily tides were observed on the dates indicated in Fig. 6. A temperature decrease in between the mentioned dates falls on semi-daily tide cycles in the Amursky Bay.
We believe that the link between the sea and the area of groundwater discharge is the upper highly permeable aquifer (pebbles and sand) and its thickness is 20 m (Chelnokov et al. 2008). This is the alluvial-marine complex extends on 30 kilometers from the Razdolnaya River mouth bar and seawaters penetrate into it (Chelnokov et al. 2008). It is known that еhe saline groundwater intrusion distance balance is mainly subject to the intensity with which aquifers are loaded with meteoric water and the difference in the density of sea and fresh water (Michael et al. 2005; Vallejos et al. 2015; Rodellas et al. 2017). Tides generate complex groundwater fluctuations in aquifers (Carr and Der Kamp 1969; Smith 2004). In turn, diurnal and semidiurnal variations in recirculated groundwater flux also have a period of tidal sea level fluctuations (Taniguchi et al. 2002; Burnett et al. 2006; Kobayashi et al. 2017). Tidal fluctuations of the water level are possible in small lagoons separated from the sea by land and even in water wells connected with the sea via the upper aquifer at a distance of many kilometers (Werner et al. 2013). If the saline groundwater intrusion meets with fresh land waters in the upper aquifer, density gradients in the transitional zone cause convective circulation and groundwater discharge occurs in the vicinity of this underground hydrological front (Smith and Turner, 2001). Thus, the main drivers for groundwater discharge increasing in the inner Razdolnaya River Estuary during freeze-up and winter runoff low period are as follows: increased proportion of seawater in the upper aquifer, slow water dynamics as a result of ice formation / low river runoff, increased duration of hydraulic head during the period of daily tides and the high hydraulic conductivity of the aquifer.
The combination of a high radium isotopes activity rate, above-zero temperature anomaly and oxygen saturation drop show that the saltwater wedge with salinity of 25.2 psu (Fig. 2) is formed in winter totally as a result of discharge of groundwater. It is known that relatively short-period seawater recirculation in the upper aquifer is accompanied by enrichment with short-lived radium isotopes 224Ra and 223Ra only (Rodellas et al. 2017). Admixing freshwater in this aquifer will bring long-lived isotopes 228Ra as well (Bear et al. 1999; Taniguchi et al. 2002; Moore 2008; Burnett et al. 2006). A simultaneous increase of concentrations of short-lived radium isotopes 224Ra and 223Ra and long-lived isotopes 228Ra can be anticipated in case of discharge of waters consisting of a mix of pore water, fresh groundwater and recirculated sea groundwater. The composition of stable isotopes δ18O and δD (Fig. 7) in the discharge zone is subject to the sea water / river water ratio. It is considered that the main reason for groundwater discharge is that recirculated water has penetrated into the upper aquifer during the winter runoff low period and further discharged into the deepest section lines of the estuary.
We have observed a special case of groundwater discharge, which is probably typical for channel type estuaries with a long low-water period. As mentioned above, the seasonal variability of Razdolnaya River discharge is large and is characterised by a 500-fold difference between winter and summer. This creates favourable conditions for seawater recirculation in the upper aquifer during the winter runoff low period. We suggest as the landward movement of seawater in coastal aquifers oxygen in the aquifer becomes depleted, and further groundwater seepage through the oxygen free layer of sediments rich in organic matter also results in oxygen depletion, similar to processes shown and discussed in other papers (Guo et al. 2020; Moore and Joye, 2021). As a result, in the course of interaction between the upper aquifer and estuary, we see oxygen saturation rates in the near-bottom layer reducing toward the estuary top, simultaneous increase of water temperatures and radium isotopes activity rates.