Indian Journal of Marine Sciences Vol. 35 (3), September 2006, pp.

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Sediment oxygen consumption in a developed coastal lagoon of the Mexican Caribbean

*David S. Valdes-Lozano, Marcela Chumacero & Elizabeth Real
Centro de Investigacin y de Estudios Avanzados, Km. 6 Antigua Carretera a Progreso, C.P. 97310, Mrida, Yucatn, Mxico. *(Email: dvaldes@mda.cinvestav.mx) Received 6 june 2005; revised 10 April 2006
Nichupte is estuarine lagoon connected to the Caribbean Sea by two channels with very high levels of organic carbon in sediments, which ranged from 1.56 to 9.29 %, with the maximum concentration at the northeastern zone, known as Bojorquez, a section with high greater anthropogenic impacts. The rate of sediment oxygen consumption (measured in the laboratory) during summer (July) was 292 mmol O2 m-2 d-1 at Bojorquez, with a mean value of 70 mmol O2 m-2 d-1. During winter (January), at the same site, the rate increased to 309 mmol O2 m-2 d-1 (average 125 mmol O2 m-2 d-1). The total average for both seasons (summer and winter) was 97 mmol O2 m-2 d-1. For the whole lagoon system (48.3 km2), the total oxygen consumption by sediments was 4.6 X 106 mol O2 d-1. During summer, the net input of oxygen from the sea to the lagoon was 1.6 X 105 mol O2 d-1, decreasing towards winter (1.5 X 105 mol O2 d-1). The oxygen input from sea to lagoon, represented only 3 % of the oxygen consumed by sediments, indicating that, if some of the oxygen sources like photosynthesis or wind re-aeration are interrupted or diminished, hypoxia might occur, particularly at Bojorquez zone. [Key words: Sediment, Nichupte, Bojorquez, oxygen consumption, BOD, lagoon, Mexican Caribbean coast]

Introduction Sediment oxygen consumption is a very important process that gives a base for oxygen demand over which other more dynamic oxygen demands (like water biochemical oxygen demand) overcome 1. In addition to that, the sediment oxygen consumption together with the nutrient and organic matter content is an indicator of the decomposition rate in sediments; this characteristic makes it an excellent indicator of organic matter pollution2. Furthermore, sediment oxygen consumption is important to develop mathematical models and thus, predict water quality 3. Since oxygen is the most important oxidant for respiration process of organic matter degradation, its concentration and distribution along sediments is critical for organic carbon decomposition and recycling of nitrogen and phosphorus 4. The Nichupte lagoon is a shallow estuarine system from the Mexican Caribbean Coast. Nichupte was a pristine lagoon and gradually become a totally modified ecosystem during last 25 years 5, 6. This estuary is surrounded by urban developments that produce a great amount of organic wastes 7,8.

Nichupte lagoon is located at the oriental coast of the Peninsula of Yucatan, Mexico (Fig. 1), is an estuary with a barrier formed by organic and marine sediments 9. The regional weather is tropical, semi humid and the tidal range is of 0.3 m. The lagoon has an area of approximately 48 km2 and a depth range of 1 and 1.5 m, excepting the channel where the main access was dredged up to 3 m of depth. During the last decade, tourist and urban developments have increased along the shore. These anthropogenic activities have brought in nutrients and organic matter to the lagoon in a direct or indirect way. The objective of the present study is to determine how much sediments contributes to the oxygen consumption in Nichupte and if the lagoon is importing or exporting oxygen to the sea, both information important because can be used for management of the system and for maintain equilibrium and healthy conditions. Materials and Methods Sediment oxygen consumption was measured taking sediment cores and incubating them in the laboratory. At the same time, the water flow in and out was measured at the two channels that connect Nichupte lagoon to the Caribbean, measuring dissolved oxygen concentration to quantify the net exchange between the lagoon and the sea, during both sampling seasons (summer and winter).

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86E 47' 30" W E

Cancun channel

86E 45' W E

21E07' 30" N E

2 4 5

Bojorquez Lagoon

Nichupte Lagoon
21E05'N E

7 8

21E05'N E

Caribbean Sea
9 10

22ENGulf of 88E87E86E

Mxico Nichupte
21EN
Lagoon

Yucatn Peninsula
Nizuc channel

86E 47' 30" W E

MEXICO

Caribbean Sea

Fig. 1.- Nichupte System Map. Sampling sites for sediments located within the system and the two channels can be observed. The 24 h cycles were carried out the two channels during July 2002 and January 2003.

The sampling was carried out during July 2002 and January 2003. A hand corer (45 mm inner diameter core, 500 mm height, Wild Co. CA USA) was used to obtain surface sediment samples at 10 sites distributed within the lagoon (Fig. 1). Sediment cores were collected in two replicates and transported immediately in acrylic tubes from the same hand corer (they were placed at darkness and a temperature of 10 C). These acrylic tubes were used for incubating the samples. The samples were incubated in the next 72 hrs. Ambient water samples were collected (1 m depth) and kept in darkness at 4 C for later analyses. A 24 hrs cycle was carried out in summer 2002 and winter 2003, where a water sample was collected every two hours interval, for estimating the oxygen exchange between the sea and the lagoon system, the flow in and out of seawater was measured using the drifting body technique 10 within two channels connecting them (Fig. 1). The dissolved oxygen and other parameters (salinity, pH, suspended solids, ammonium, nitrite, nitrate, phosphate and silicate) detailed further on, were quantified in these samples.

The oxygen consumption within the sediments was measured by incubation at the laboratory according to Nakamura 2 using a model 55 YSI oxygen meter. This method analyzes the oxygen concentration of the supernatant water of the cores kept on a moderated agitation during 2 hours, in the darkness and at 25 C. At the same time, a control was incubated without sediment to estimate the oxygen consumption and the difference was considered as the net consumption by sediments. In all the experiments the water was saturated with O2 at the beginning, by bubbling air for 15 min. before the incubation. The physical and chemical characteristics of the top 5 cm of sediments were analyzed as follow: organic carbon content by wet oxidation with dichromate/H2SO4 and back titration of the excess with Fe SO411, grain-size analysis (sand, silt and clay) was carried out with sieves and the pipette method for fine fractions 10, porosity was estimated by weight loss after drying at 90 C 11; pH and redox potential with a potentiometer and glass and platinum electrodes, respectively 12, total nitrogen and phosphorus by wet oxidation with potassium persulfate on basic and acidic conditions, respectively 13-15. In the interstitial water extracted under nitrogen environment 16, the total sulfide was determined by oxidation with iodine in excess 17. Dissolved oxygen concentration of water samples of lagoon and channels were estimated with the Winkler titration method 18 ; oxygen saturation using Garcia & Gordon 19 equations; salinity with an induction salinometer Kahlsico RS-9, pH with an electrode and a potentiometer; suspended solids using a gravimetric method where 1 L of the sample is filtered through a micro fiber glass filter 15. In addition, the concentration of ammonium, nitrite, nitrate, phosphates and silicates were also determined 18 . The biochemical oxygen demand was measured from all the lagoon samples by incubating for 5 days and titrating the oxygen with the method mentioned above. The relationships between the sediment oxygen consumption and the other parameters were evaluated with correlation analyses. To test differences between July/2002 and January/2003 samplings and among the north, center and south regions, different types of variance analysis were run using the software Statistica 20. Results Table 1 shows the values for the seawater parameters at the 10 sampled sites in both seasons. The suspended solids increased in winter, however,

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their concentration were low, i.e. less than 5 mg l-1. Part of the reason for the suspended solid behavior was the stabilization of sediments by aquatic vegetation. Nutrient concentrations were very low, except for silicates. The characteristics of the sediments sampled during summer 2002 and winter 2003 are summarized in Table 2. The grain-size analysis indicated that sand was the main fraction for all the regions (north, center and south), followed by clay and silt. The chemical analysis indicated high organic carbon content in the surface sediments (the mean value was 3.7 2.0 %). Very anoxic conditions (mean redox potential 320 111 mV), PH values < 7 and high sulfide concentrations with an average of 2.0 0.8 mM in the interstitial water of lagoon sediments, were found as a result of the oxidation of organic matter. The sediment oxygen consumption values varied in different regions of the lagoon (0-309 mmol O2 m-2 d-1)
Sample

but did not differ greatly between the first and the second sampling seasons (Table 2). The rate of oxygen consumption by sediments reached 292 mmol O2 m-2 d-1 at station No. 3 in the summer, while the mean value in the lagoon in this season was 70 85 mmol O2 m-2 d-1. In the winter season the consumption raised to 309 mmol O2 m-2 d-1 again in station No. 3, while the total average for the whole lagoon system was 125 108 mmol O2 m-2 d-1. The average rate for both seasons was 97 100 mmol O2 m-2 d-1. Very high variance in the oxygen consumption in the lagoon was found, meaning that the sediment conditions are very different from one place to another. For the total area of the whole lagoon system (48.3 km2), the total oxygen consumption by sediments was estimated in 4.6 X 106 mol O2 d-1. During both sampling periods, the oxygen flux in the lagoon channels was of similar magnitude. In summer the importation was 1.6 X 105 mol O2 d-1, while in winter 1.5 X 105 mol O2 d-1.

Table 1.- Physical and chemical characteristics of the water in the Nichupte lagoon, Quintana Roo, Mexico
Temp. Salinity pH Dissolved Oxygen BOD Ammonium Nitrite Nitrate Phosphate Silicate Total Organic Inorganic oxygen saturation suspended suspended suspended solids solids solids (C) (PSU) (:mol l-1) (%) (ml l-1) (:M) (:M) (:M) (:M) (:M) (mg l-1) (mg l-1) (mg l-1) 32.5 33.3 32.9 32.9 33.2 33.7 32.8 32.6 33.2 33.2 33.0 0.3 33.35 30.40 31.06 32.32 27.22 30.93 25.01 23.86 32.31 35.83 30.23 3.58 7.88 7.89 7.75 7.79 7.87 7.70 7.87 7.89 7.83 7.81 7.82 0.06 208 166 142 157 186 121 165 216 180 177 172 27 110 88 75 83 97 64 84 109 96 96 90 14 0.34 0.34 0.51 0.28 0.45 0.23 0.23 0.23 0.11 0.17 0.29 0.12 2.97 8.07 9.66 3.11 3.50 3.09 4.46 1.69 1.98 1.48 4.00 2.60 0.14 0.22 0.14 0.06 0.22 0.14 0.16 0.12 0.05 0.02 0.13 0.06 1.28 1.15 0.45 0.46 1.46 0.76 1.60 0.61 0.18 0.20 0.82 0.49 0.07 0.04 0.02 0.04 0.05 0.04 0.07 0.07 0.05 0.08 0.05 0.02 8.39 15.38 11.84 16.52 16.22 16.74 18.67 13.64 13.37 4.55 13.53 4.08 1.1 0.8 2.2 1.8 1.0 1.6 1.6 1.0 2.5 2.1 1.6 0.5 0.7 0.7 1.4 0.9 0.7 0.9 0.9 0.8 1.1 0.9 0.9 0.2 0.4 0.1 0.8 0.9 0.3 0.6 0.7 0.2 1.3 1.2 0.7 0.4

July 2002 1 2 3 4 5 6 7 8 9 10 Average S.D. January 2003 1 2 3 4 5 6 7 8 9 10 Average S.D.

23.6 24.7 23.0 22.8 23.1 22.9 22.7 23.9 23.3 23.4 23.3 0.6

27.29 29.30 27.78 26.99 24.62 25.71 24.90 28.10 26.99 27.98 26.97 1.41

7.21 7.45 7.69 7.99 8.15 8.01 8.10 8.25 8.17 8.17 7.92 0.33

177 182 185 189 201 193 191 253 191 233 200 23

78 83 81 82 87 83 82 113 84 103 88 11

0.73 1.01 1.41 1.01 0.51 0.96 0.56 0.51 0.79 0.73 0.82 0.27

42.13 2.37 7.95 4.57 4.64 3.68 11.10 2.53 2.73 2.89 8.46 11.53

0.81 0.18 0.37 0.23 0.42 0.29 0.45 0.12 0.11 0.04 0.30 0.21

1.90 0.94 1.32 1.14 2.85 1.55 2.70 0.70 0.57 0.51 1.42 0.79

0.02 0.02 0.01 0.01 0.02 0.02 0.02 0.03 0.00 0.01 0.02 0.01

16.40 8.15 7.64 11.00 10.68 11.74 12.36 9.90 7.84 7.56 10.33 2.64

7.3 2.3 7.9 1.7 2.2 1.4 8.4 3.5 1.7 1.5 3.8 2.7

3.4 1.6 3.3 0.9 1.6 1.2 2.4 2.3 1.4 1.1 1.9 0.8

3.9 0.7 4.6 0.8 0.6 0.2 6.0 1.2 0.3 0.4 1.9 2.0

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The oxygen exchange was greater at North (Cancun) channel which is the deepest and with the more direct connection to the sea. In this channel, the oxygen input was 1.5 X 105 mol O2 d-1 in July 2002 (summer) and 1.8 X 105 mol O2 d-1 in January 2003 (winter). While at the South (Nizuc) channel, the balance in July was the input of only 0.1 X 105 mol O2 d-1 and for January the output of 0.3 X 105 mol O2 d-1 (this channel is shallow, long and sinuous). Discussion During the sampling period 2002-2003, the water characteristics were very similar to those reported previously for this lagoon system 7, 8 . As expected, temperature and salinity decreased between the sampling carried out in July and the one in January because of more sunlight exposure and less precipitation during summer. Nutrient levels could be classified as

normal concentrations for coastal lagoons located at this region 21-24; dissolved inorganic nitrogen varied between 3 and 10 Molar ( M), being the ammonium fraction the most important (> 90 %); phosphates concentrations were very low (< 0.1 M) caused mainly by a strong ion adsorption by the calcareous sediments 25; and silicates were present at concentrations greater than 10 M, due to inputs of ions from water springs 26. The oxygen saturation was below 100 % at both seasons, suggesting that the production of O2 gas by photosynthesis is less than consumption. The organic matter, estimated as Biochemical Oxygen Demand, was less than 1 ml l-1 at the majority of the sites. Although the average value was greater on the second sampling, still they were acceptable as very clean water 15.

Table 2.- Physical, chemical characteristics of sediments and sediment oxygen consumption (SOC) in the Nichupte lagoon, Quintana Roo, Mexico.
Sample Total sulfide (mM) 1.7 2.1 1.2 1.9 1.3 1.3 1.5 1.7 1.6 1.7 1.6 0.3 Organic carbon (%) 1.56 3.24 7.39 2.68 2.86 3.17 3.42 1.56 2.37 3.17 3.14 1.55 Total phosphorus (:mol g-1) 2.9 1.8 4.2 1.8 1.3 1.6 1.6 0.6 1.3 4.3 2.1 1.2 Total nitrogen (:mol g-1) 127.4 128.2 250.6 191.1 204.5 153.6 230.3 92.7 157.9 144.3 168.1 47.3 Redox potential (mV) -310 -299 -320 -308 -318 -329 -322 -307 -318 -792 -362 144 pH Sand (%) 6.16 6.29 6.12 6.47 6.32 6.33 6.37 6.55 6.33 6.25 6.32 0.12 82 76 74 76 60 79 60 80 72 74 73 7 Silt (%) 9 11 10 10 13 9 12 10 12 11 11 1 Clay (%) 9 13 16 14 27 11 28 10 16 15 16 6 SOC (mmol O2 m-2 d-1) 55 26 292 0 136 55 5 0 34 100 70 85

July, 2002 1 2 3 4 5 6 7 8 9 10 Average S. D. January, 2003 1 2 3 4 5 6 7 8 9 10 Average S. D.

1.5 2.0 2.8 1.9 3.4 1.3 2.6 3.7 1.4 4.3 2.5 1.0

5.29 4.00 7.50 1.85 9.29 2.81 3.22 3.29 1.92 2.74 4.19 2.34

1.8 4.8 3.5 1.6 2.4 1.1 1.5 2.1 1.1 1.7 2.2 1.1

75.1 96.9 111.3 64.6 85.4 82.9 49.2 102.5 62.3 60.6 79.1 19.2

-222 -284 -285 -275 -307 -262 -299 -297 -259 -296 -278.5 24.0

7.30 7.27 7.23 7.35 7.06 7.19 7.21 7.06 7.28 7.07 7.2 0.1

57 61 69 66 57 45 44 60 65 62 58.6 7.9

13 30 18 21 15 16 14 20 15 28 19 36 24 32 17 23 15 20 18 20 16.8 24.6 3.0 6.2

0 268 309 200 62 26 64 0 104 215 125 108

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Physical and chemical characteristics of sediments Sediments in the lagoon are mostly composed by sand and clay, mixture with very low permeability that decreases rates of reactions and processes 12. Organic carbon content in the surface sediments was greater than any concentration reported for pristine lagoons from the same area 23, 24, 27, although less than those reported for other tropical coastal lagoons with mangroves 28. This high content of biogenic material was reflected also by the high total phosphorus and total nitrogen concentration, particularly total nitrogen. Similar concentrations have been reported for other regional systems affected by municipal wastes

like Chelem and Ria Lagartos lagoons in the north coast of the Yucatan Peninsula 23,29. The highest concentrations of organic matter, nitrogen and phosphorus, were measured towards northeast sites (i.e. Bojorquez, site 3) with intense tourist activity, even though the organic matter peak corresponded to site 5 toward the west (next to Cancun City). Very high concentrations of organic matter in the sediments has led to very anoxic conditions resulting in negative redox potential, acid PH and high sulfide concentrations in the interstitial water of lagoon sediments, a usual characteristic in systems with submerged vegetation and /or mangroves 28, 30.

' 86 47' 30" W

' 86 45' W

CANCUN

- 21 07' 30" N

- 21 05' N

21 05' N -

CARIBBEAN SEA
Fig. 2.- Sediment oxygen consumption (in mmol O2 m-2 d-1) isolines at Nichupte lagoon. Average for both sampling time periods.

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Biochemical oxygen demand-5 ml l -1

1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 -50

50

100

150

200

250
-2 -1

300

350

Sediment oxygen consumption mmol m d

-1

6 5 4 3 2 1 0 -50

50

100

150

200

250
-2

300 d
-1

350

Sediment oxygen consumption mmol m

Fig. 3.- The significantly correlation A) between biochemical oxygen demand (BOD-5) in the water and the sediment oxygen consumption at Nichupte lagoon (r = 0.63, p < 0.05), B) between total phosphorous in sediment and the sediment oxygen consumption at Nichupte lagoon (r = 0.62, p < 0.05). Table 3.- Oxygen consumption by the sediments at different areas Area / reference South River, North Carolina, USA 33 Neuse River, North Carolina, USA 33 Texas coast, USA 34 San Francisco Bay, CA, USA 35 Fourleague Bay, LA, USA 36 Patuxent River, MD, USA 37 Cadiz Bay, Spain38 Willamette River, Portland, Oregon39 Chesapeake Bay, USA 40 Odense Fjord, Denmark41 Mobile Bay, Alabama, USA 3 Rouge River, Michigan, USA 42 Port Phillip Bay, Australia4 Thames River Estuary, UK32 Upper Klamath Lake, OR, USA 43 Mid-Atlantic Bight, NJ, USA 44 Seto Sea, Japan2 Cauca River, Colombia45 Nichupte, Mexico (this work) Consumption (mmol O2 m-2 d-1) 22-84 22-59 34-159 13-22 0-106 25-72 69-234 41-128 0.0-28 31-153 3-41 31-169 3-28 13-241 50-53 166 34-72 44-228 6-309

The lowest pH value (6.12) and a very negative redox potential (-320 mV) were recorded for site 3 (at Bojorquez zone), as a consequence of the oxidation of organic matter, even with the presence of macrophytes which have been reported to raise the redox potential 31. The sediment oxygen consumption in Nichupte lagoon had a large spatial, but low temporal variation; figure 2 shows the lagoon map with isolines of the average oxygen consumption rates. The isolines clearly demonstrate the Bojorquez region (station No. 3, northeast of the lagoon system) as the zone with highest oxygen consumption. As mentioned above, this region is surrounded by tourist developments (hotels, restaurants and golf fields) and the water circulation is very poor (previous studies reported a water residence time of 2.7 years 7, 8). This long water residence time causes accumulation of organic matter in the sediments which increase the demand of oxygen for its degradation. The rates of sediment oxygen consumption were positively and significantly correlated with both, water BOD (r = 0.63, p < 0.05) and total phosphorus concentration of sediments (r = 0.62, p < 0.05), suggesting an intrinsic connection between the processes occurring in water and sediments (Fig. 3 A and B). Table 3 shows the oxygen consumption by sediments at different studied sites, the findings of this study are quite similar to those reported previously. However, at the north region of Nichupte (Bojorquez), the oxygen consumption was greater than the majority of the early results (Table 3). The peak value reported was 241 mmol O2 m-2 d-1 corresponding to the River Tamesis estuary 32. This result reinforces the conclusion of that, in the Bojorquez region, there is a great demand of oxygen consumption by the sediments. The flux estimations of dissolved oxygen in the two channels that connect the lagoon with the sea indicate a net input of this gas from the sea towards the lagoon, during both summer and winter, which means that Nichupte Lagoon is an oxygen importer system. According to the estimated amount of oxygen imported from the sea, and the oxygen consumption by the sediments of the whole lagoon, the first one represents only a 3 % of the oxygen consumed by sediments. This clearly indicates that the lagoon is in a critical condition and that, if some of the major oxygen sources (photosynthesis and wind re-aeration) might be interrupted or diminished, dissolved oxygen will decrease and hypoxia might cause adverse ecological consequences, particularly at Bojorquez zone, where the sediment oxygen consumption was greater than at the other sites.

Total phosphorous in sediment mol g

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