人类活动影响下的龙口海岸带海底地下水排泄通量研究

在沿海地区,以²²³Ra和²²⁴Ra为示踪剂建立的镭质量平衡模型已广泛应用于海底地下水排泄量(SGD)的研究中,然而目前国内外关于在人类活动复杂影响较大情况下的SGD研究却极为少见。本文对比研究了在有防渗墙(A区)和填海造陆(B区)两种不同人为因素影响下的龙口海岸带水体表现年龄、海底地下水排泄量及其携带的氮磷营养盐通量。结果表明,A区平均水体表现年龄为14.26 d,B区平均水体表现年龄为10.64 d。此外,B区沿岸地下水以及近岸海水中的Ra活度均普遍高于A区,而盐度低于A区。在SGD方面,A区的SGD速率为1.26~1.60 cm·d^-1,B区为1.43~1.82 cm·d^-1,考虑SGD在评估方法上存在一定的误差,因此两个区域的SGD速率相差不大。但与我国其他自然海域相比,这两个区域的SGD速率均处于较低水平。此外,B区的氮磷营养盐浓度普遍高于A区,而且由SGD驱动的氮磷营养盐通量不同,地下水输入的不平衡的营养盐极易改变龙口海域的营养盐结构,对海洋生态环境产生不利影响,这也进一步证实SGD在沿海生态环境以及水体污染治理中的重要地位。     

Marsh-water column interactions in two Louisiana estuaries. II. Nutrient dynamics

The exchange of dissolved nutrients between marshes and the inundating water column was measured using throughflow marsh flumes built, in two microtidal Louisiana estuaries: the Barataria Basin estuary and Fourleague Bay. The flumes were sampled between September 1986 and April 1988, coincident with an extended period of low sea level on the Louisiana coast. The Barataria Basin estuary is in the later, deteriorating stage of the deltaic cycle, characterized by low freshwater inputs and subsiding marshes. Both brackish and saline marshes supplied dissolved organic nitrogen (DON), inorganic nitrogen (ammonium + nitrate + nitrite = DIN), dissolved organic carbon (DOC), and total nitrogen (as total Kjeldahl nitrogen = TKN) to the water column. The export of DIN is probably related to the N accumulated in earlier stages of deltaic development and released as these marshes deteriorate. Coastal brackish marshes of Fourleague, Bay, part of an accreting marsh system in an early, developmental stage of the deltaic cycle, exported TKN to the open water estuary in all samplings. This marsh apparently acted as a short-term buffer of DIN by taking up NH₄ ⁺ in spring, when baywide concentrations were high, and supplying DIN to the estuary in summer and fall, when concentrations, in the bay were lower. Differences in phosphorus (P), DOC, and DON fluxes between these two estuaries were also observed. The Fourleague Bay site exported soluble reactive phosphorus (SRP) and total phosphorus (TP) and imported DOC. This P export may be related to remobilization of sediment-bound riverine P by the reducing, soils of the marshes. Fluxes of SRP at the Barataria Basin sites were variable and low while DOC was imported. Most imports of dissolved nutrients were correlated with higher upstream [source] concentrations, and flux rates were fairly consistent throughout the tide. Dissolved nutrient exports, did not correlate with upstream concentrations, though, and in many cases the flux was dominated by early, flood tide nutrient release. This pulsed behavior may be caused by rapid diffusion from the sediments early in the tidal cycle, when the sediment-water concentration gradient is largest. Interestuary differences were also seen in particulate organic matter fluxes, as the Fourleague Bay marsh exported POC and PON during all samplings while Barataria Basin imported these nutrients. In general, the magnitude and direction of nutrient exchanges in Louisiana marshes, seem to reflect the deltaic successional stage of the estuary.     

用镭-226示踪胶州湾的海底地下水排泄

海底地下水排泄（SGD）是全球水循环的一个组成部分,其输送的溶解物质不仅参与海洋的生物地球化学循环,而且影响近岸海域的生态环境。为了评估胶州湾海底地下水排泄状况,通过建立胶州湾内海水中²²⁶Ra的质量平衡模型来计算海底地下水排泄通量。胶州湾海水中²²⁶Ra的源主要有河流的输入、沉积物扩散输入和地下水的输入,海水系统在稳定状态下,这几种源应该与湾内海水和湾外海水的混合损失达到平衡。除了将地下水输入作为未知项外,对其他源和汇逐个进行量化,计算得知：2011年9-10月胶州湾的海底地下水排泄通量为7.85×10⁶ m³·d^-1;2012年4-5月胶州湾的海底地下水排泄通量为4.72×10⁶ m³·d^-1。在此基础上,对地下水输入胶州湾的营养盐进行了评价。     

Submarine Groundwater Discharge Estimates Using Radium Isotopes and Related Nutrient Inputs into Tauranga Harbour (New Zealand)

Land-based pollutants such as fertilizers and wastewater can infiltrate into aquifers and discharge into surrounding coastal water bodies as submarine groundwater discharge (SGD). Oceanic islands, with a large coast length to land area ratio, may be hot spots of SGD into the global ocean. Although SGD may be a major pathway of dissolved nutrients, carbon and metals to coastal waters, studies have been limited due to the difficulties in measuring this often diffuse process. This study used radium isotopes (²²³Ra, ²²⁴Ra, ²²⁶Ra) to investigate SGD and the associated fluxes of nutrients into Tauranga Harbour, New Zealand. We calculated the apparent water mass ages of the harbour to be between ~4.1 and 7.8 days, which was similar to a previous numerical model of ~2–8 days. A ²²⁶Ra mass balance was constructed to quantify SGD fluxes at the harbour scale. A minimum SGD flux rate of 0.53 cm day^?1 was calculated by using the maximum groundwater end-member value from 22 sample sites. However, using the geometric mean from these samples as a representative end-member, a final value of 2.83 cm day^?1 or a flux of 3.09 × 10⁶ m³ day^?1 was calculated. These values were between ~1 and 2.8 times greater than all the major river and creeks discharging into the harbour during the sampling period. Due to the higher observed nutrient concentrations in groundwater, the SGD-derived dissolved inorganic nitrogen (DIN), dissolved organic nitrogen (DON) and total dissolved phosphorus (TDP) fluxes were calculated to be 1.07, 0.87 and 0.05 mmol m² day^?1, respectively. These SGD inputs were ~5 times (for nitrogen) and ~8 times (for phosphorus) greater than the input from surrounding rivers and streams. The average N:P ratio in groundwater samples was 36:1 (which was greatly in excess of the Redfield ratio of 16). The harbour water had a N:P ratio of ~17:1. A positive relationship between radium isotopes and N:P ratios in the harbour further supported the hypothesis that SGD can have major implications for primary production, including recurrent algal bloom events which occur in the harbour. We suggest SGD as a major driver of nutrient dynamics in Tauranga Harbour and potentially other similar coastal lagoon systems and estuaries on oceanic islands.     

Assessment of Submarine Groundwater Discharge (SGD) as a Source of Dissolved Radium and Nutrients to Moorea (French Polynesia) Coastal Waters

Previous work has documented large fluxes of freshwater and nutrients from submarine groundwater discharge (SGD) into the coastal waters of a few volcanic oceanic islands. However, on the majority of such islands, including Moorea (French Polynesia), SGD has not been studied. In this study, we used radium (Ra) isotopes and salinity to investigate SGD and associated nutrient inputs at five coastal sites and Paopao Bay on the north shore of Moorea. Ra activities were highest in coastal groundwater, intermediate in coastal ocean surface water, and lowest in offshore surface water, indicating that high-Ra groundwater was discharging into the coastal ocean. On average, groundwater nitrate and nitrite (N + N), phosphate, ammonium, and silica concentrations were 12, 21, 29, and 33 times greater, respectively, than those in coastal ocean surface water, suggesting that groundwater discharge could be an important source of nutrients to the coastal ocean. Ra and salinity mass balances indicated that most or all SGD at these sites was saline and likely originated from a deeper, unsampled layer of Ra-enriched recirculated seawater. This high-salinity SGD may be less affected by terrestrial nutrient sources, such as fertilizer, sewage, and animal waste, compared to meteoric groundwater; however, nutrient-salinity trends indicate it may still have much higher concentrations of nitrate and phosphate than coastal receiving waters. Coastal ocean nutrient concentrations were virtually identical to those measured offshore, suggesting that nutrient subsidies from SGD are efficiently utilized.     

Submarine groundwater discharge enhances primary productivity in the Yellow Sea,China:Insight from the separation of fresh and recirculated components

Submarine groundwater discharge(SGD)is being increasingly recognized as a significant source of nutri-ent into coastal waters,and generally comprises two components:submarine fresh groundwater dis-charge(SFGD)and recirculated saline groundwater discharge(RSGD).The separate evaluation of SFGD and RSGD is extremely limited as compared to the conventional estimation of total SGD and associated nutrient fluxes,especially in marginal-scale regions.In this study,new high-resolution radium isotopes data in seawater and coastal groundwater enabled an estimation of SGD flux in a typical marginal sea of the Yellow Sea.By establishing 226Ra and 228Ra mass balance models,we obtained the SGD-derived radium fluxes,and then estimated the SFGD and RSGD fluxes through a two end-member model.The results showed that the total SGD flux into the Yellow Sea was equivalent to approximately 6.6 times the total freshwater discharge of surrounding rivers,and the SFGD flux accounted for only 5.2％-8.8％of the total SGD.Considering the nutrient concentrations in coastal fresh and saline groundwater,we obtained the dissolved inorganic nutrient fluxes(mmol m-2 yr-1)to be 52-353 for nitrogen(DIN),0.21-1.4 for phosphorus(DIP),34-226 for silicon(DSi)via SFGD,and 69-262 for DIN,1.0-3.9 for DIP,70-368 for DSi via RSGD,with the sum of nutrient fluxes equaling to(1.8-9.3)-fold,(1.3-5.6)-fold and(2.0-9.5)-fold of the riverine inputs.Compared to the conventional estimation of the total SGD flux,the nutrient fluxes derived from the separation of SFGD and RSGD were(1.6-2.1),(1.6-1.8)and(4.0-4.9)times lower for DIN,DIP and DSi,respectively,indicating that the estimates by separating SFGD and RSGD could be conservative and representative results of the Yellow Sea.Furthermore,we suggested that SGD played an important role in nutrient sources among all the traditional nutrient inputs sources,providing 15％-48％,33％-68％and 14％-43％of the total DIN,DIP and DSi input fluxes into the Yellow Sea,and the high nutrient stoichiometric ratios(i.e.,DIN/DIP)in SGD probably contributed to the increasing ratios in the Yellow Sea.In addition delivering large amounts of nutrient into the Yellow Sea,SGD would create primary productivity of 10-49,1.6-6.8 and 8.8-42 g C m-2 yr-1 based on N,P and Si,which were equivalent to 5.2％-27％,0.9％-3.7％and 4.7％-23％of the total primary productivity,respectively.In par-ticular,the SFGD-derived DIN flux can be converted to primary productivity of 4.2-28 g C m-2 yr-1 thus demonstrating the disproportionately large role of SFGD in ecological environment of the Yellow Sea rel-ative to its flux.Therefore,we conclude that SGD,particularly SFGD,plays an important role as a nutrient source for the Yellow Sea,and not only affects nutrient budgets and structures but also enhances the pri-mary productivity.     

Nitrogen pools in Georgia coastal waters

The amount of nitrogen present as ammonia, nitrate, nitrite, dissolved organic nitrogen, and particulate nitrogen was determined for nearshore Georgia shelf waters and for tidal water inundating a 0.5 hectare dikedSpartina alterniflora salt marsh in the adjacent estuary. Concentrations of ammonia, nitrate, and nitrite were comparatively low in offshore water (<2.2 μg-at N/1), and in high tide water in the marsh (<9.9 μg-at N/1). High concentrations of ammonia, up to 73.4 μg-at N/1, were measured in low tide water draining from marsh. The largest pools of nitrogen in offshore water and in high tide water in the marsh creek were dissolved organic nitrogen (DON) (2.5 to 20.4 μg-at N/1) and particulate nitrogen (PN) (0.1 to 30.0 μg-at N/1). Concentrations in marsh creek water at low tide were higher, ranging from 4.4 to 38.0 μg-at N/1 for DON and from 13.0 to 239.0 μg-at N/1 for PN. Comparisons of the average concentrations of dissolved and particulate forms of nitrogen in the marsh tidal creek during flood and during ebb tide suggested no net movement of the inorganic nitrogen nutrients, a net influx of PN to the marsh, and a net outflux of DON from the marsh.     

Using Optical Properties to Quantify Fringe Mangrove Inputs to the Dissolved Organic Matter (DOM) Pool in a Subtropical Estuary

Dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) optical properties were analyzed along two estuarine river transects during the wet and dry seasons to better understand DOM dynamics and quantify mangrove inputs. A tidal study was performed to assess the impacts of tidal pumping on DOM transport. DOM in the estuaries showed non-conservative mixing indicative of mangrove-derived inputs. Similarly, fluorescence data suggest that some terrestrial humic-like components showed non-conservative behavior. An Everglades freshwater-derived fluorescent component, which is associated with soil inputs from the Northern Everglades, behaved conservatively. During the dry season, a protein-like component behaved conservatively until the mid-salinity range when non-conservative behavior due to degradation and/or loss was observed. The tidal study data suggests mangrove porewater inputs to the rivers following low tide. The differences in quantity of DOM exported by the Shark and Harney Rivers imply that geomorphology and tidal hydrology may be a dominant factor controlling the amount of DOM exported from the mangrove ecotone, where up to 21 % of the DOC is mangrove-derived. Additionally, nutrient concentrations and other temporal factors may control DOM export from the mangroves, particularly for the microbially derived fluorescent components, contributing to the seasonal differences. The wet and dry season fluxes of mangrove DOM from the Shark River is estimated as 0.27?×?10⁹ mg C d^?1 and 0.075?×?10⁹ mg C d^?1, respectively, and the Harney River is estimated as 1.9?×?10⁹ mg C d^?1 and 0.20?×?10⁹ mg C d^?1.     

Insights into estuarine benthic dissolved organic carbon (DOC) dynamics using δC-DOC values, phospholipid fatty acids and dissolved organic nutrient fluxes

Benthic dissolved organic carbon (DOC) flux rates and changes in DOC isotope ratios, along with nutrient fluxes, phospholipid fatty acids concentration and carbon isotope ratios were measured in productive estuarine sediments over a diel cycle to determine the mechanisms driving benthic-pelagic coupling of DOC. There was uptake of DOC during the dark and efflux during the light at all sites. DOC uptake rates were related to benthic respiration (dark O₂ uptake) and effluxes were coupled to the trophic status (ratio of production to respiration) of the sediments. Highest uptake and efflux rates were observed at two high nutrient concentration sites. The DOC:DON ratio of water column dissolved organic matter (DOM) decreased during the dark and increased during the light indicating preferential uptake and release of carbon rich dissolved organic matter. The calculated carbon isotope ratio of the DOC taken up by the benthos was significantly more depleted than the bulk water column DOC pool, suggesting preferential uptake of selected components of the water column DOC pool. Generally the isotope ratio of the DOC released during the light was more enriched than that taken up during the dark, which suggests that the benthos has the potential to significantly alter the estuarine DOC pool. Uptake and efflux were coupled to respiration and algal grazing/mineralization, therefore increased nutrient loading may shift the composition of the estuarine DOC pool through changes in the magnitude of benthic DOC fluxes. A combination of biological (diel shifts in DOC production and consumption) and abiotic processes (flocculation) appear to be driving the observed benthic DOC dynamics at the study sites. This study was the first to measure carbon isotopic changes in the water column DOC pool due to benthic processes, and shows that the benthos can alter the estuarine DOC pool through diel differences in DOC uptake and efflux.     

Dissolved organic matter (DOM) export to a temperate estuary: seasonal variations and implications of land use

Inputs of dissolved carbon, nitrogen, and phosphorus were assessed for an estuary and its catchment (Horsens, Denmark). Seasonal patterns in the concentrations of DOM in the freshwater supply to the estuary differed depending on the soil and drainage characteristics of the area. In streams draining more natural areas the, patterns observed were largely driven by seasonal temperature fluctuations. The material exported from agricultural areas was more variable and largely controlled by precipitation events. Positive exponential relationships were found between the nitrogen and phosphorus loading, and the percentage of catchment area used for agriculture. Colored DOM (CDOM) loading measurements were found to be a good predictor of dissolved organic carbon (DOC) loading across the different subcatchments, offering a rapid and inexpensive alternative of operationally monitoring DOC export. For all the dissolved nutrient inputs to the estuary, dissolved inorganic nitrogen (DIN) and dissolved organic phosphorus dominated the loadings. Although 81% of the nitrogen annually supplied to the estuary was DIN, 83% of the nitrogen exported from the estuary was dissolved organic nitrogen (DON). Results show that increasing the area of the catchment covered by forest and natural pastures would have a positive effect on the trophic status of the estuary, leading to a considerable decrease in the phosphorus loading and a shift in the nitrogen loading from DIN to DON. Such a change in land use would also increase the export of DOC and CDOM to the estuary having the potential to increase oxygen consumption and reduce the photic depth.     

Balance of Catchment and Offshore Nutrient Loading and Biogeochemical Response in Four New Zealand Coastal Systems: Implications for Resource Management

Nutrient mass balance analyses are a way of obtaining ‘whole system’ viewpoints on coastal biogeochemical functions and their forcing. Seasonal mass balances are presented for four large bay systems in New Zealand (NZ), with the aim of showing how they can inform coastal management. Freshwater volumes, and surface and groundwater, wastewater and atmospheric inorganic and organic nitrogen (N) and phosphorus (P) were balanced with levels of salinity, N and P from ocean surveys, used to determine non-conservative N and P fluxes and, via stoichiometry, carbon (C) fluxes. For Golden and Tasman Bays and Hauraki Gulf, exchange with adjacent shelf waters usually dominated total N supply (80–85%). In contrast, for the Firth of Thames, 51% of total N and 85% of dissolved inorganic N supply originated from its agricultural catchment. Net ecosystem metabolism (NEM; balance of autotrophy and heterotrophy) of Golden and Tasman Bays and Hauraki Gulf was usually nearly balanced. In contrast, Firth NEM was highly seasonally variable, often exhibiting strong heterotrophy coincident with expression of respiration-related stressors (low O₂ and high DIC/low pH). Denitrification accounted for about 51% of total N export across the four systems, signifying its importance as a eutrophication-regulating ecosystem service. Budgets made 12 years apart in the Firth showed decreased denitrification efficiency, coincident with large increases in system N and phytoplankton. The findings for land-ocean nutrient balance, NEM and denitrification showed how mass balance budgeting can inform coastal management, including inventories of nutrient inputs, balances of oceanic and terrestrial nutrient loading, and potential for risk associated with biogeochemical responses.     

Seasonal Alternation Between Groundwater Discharge and Benthic Coupling as Nutrient Sources in a Shallow Coastal Lagoon

Submarine groundwater discharge (SGD) is now recognized as an important source of nutrients and freshwater to some coastal environments. We studied a shallow coastal lagoon (Little Lagoon, AL, USA) in the northern Gulf of Mexico that lacks riverine inputs but has been suspected to receive significant SGD. We observed persistent salinity gradients between the east and west ends of the lagoon and the pass connecting it to the Gulf of Mexico. Covariance between salinity in the lagoon and the groundwater tracer ²²²Rn indicated that SGD was responsible for the salinity gradients and is the primary source of freshwater to the lagoon. Cluster analysis of 246 biweekly samples based on temperature, salinity, and two proxies of SGD revealed two hydrographic regimes with different drivers for nutrient inputs. In samples characterized by high discharge and low temperatures (generally December–April), total nitrogen (TN) was negatively correlated with salinity, while total phosphorus (TP) was positively correlated with temperature. Total nitrogen in the groundwater was very high (0.36–4.80 mM) while total phosphorus was relatively low (0.3–2.3 μM), consistent with SGD as the source of TN during the high-discharge periods. In periods with low discharge and higher temperatures (approx. May–November), TN and TP had strong positive correlations with temperature and are inferred to originate from benthic efflux. Seasonal changes in nutrient stoichiometry in the lagoon water column also indicate an alternation between low TN/TP sediments and high TN/TP groundwater as the primary sources of nitrogen in this system.     

Fluvial Fluxes of Water, Suspended Particulate Matter, and Nutrients and Potential Impacts on Tropical Coastal Water Biogeochemistry: Oahu, Hawai‘i

Baseflow and storm runoff fluxes of water, suspended particulate matter (SPM), and nutrients (N and P) were assessed in conservation, urban, and agricultural streams discharging to coastal waters around the tropical island of Oahu, Hawai‘i. Despite unusually low storm frequency and intensity during the study, storms accounted for 8–77% (median 30%) of discharge, 57–99% (median 93%) of SPM fluxes, 11–79% (median 36%) of dissolved nutrient fluxes and 52–99% (median 85%) of particulate nutrient fluxes to coastal waters. Fluvial nutrient concentrations varied with hydrologic conditions and land use; land use also affected water and particulate fluxes at some sites. Reactive dissolved N:P ratios typically were ≥16 (the ‘Redfield ratio’ for marine phytoplankton), indicating that inputs could support new production by coastal phytoplankton, but uptake of dissolved nutrients is probably inefficient due to rapid dilution and export of fluvial dissolved inputs. Particulate N and P fluxes were similar to or larger than dissolved fluxes at all sites (median 49% of total nitrogen, range 22–82%; median 69% of total phosphorus, range 49–93%). Impacts of particulate nutrients on coastal ecosystems will depend on how efficiently SPM is retained in nearshore areas, and on the timing and degree of transformation to reactive dissolved forms. Nevertheless, the magnitude of particulate nutrient fluxes suggests that they represent a significant nutrient source for many coastal ecosystems over relatively long time scales (weeks–years), and that reductions in particulate nutrient loading actually may have negative impacts on some coastal ecosystems.     

A Biogeochemical View of Estuarine Eutrophication: Seasonal and Spatial Trends and Correlations in the Delaware Estuary

The Delaware River and Bay Estuary is one of the major urbanized estuaries of the world. The 100-km long tidal river portion of the estuary suffered from major summer hypoxia in the past due to municipal and industrial inputs in the urban region; the estuary has seen remarkable water quality improvements from recent municipal sewage treatment upgrades. However, the estuary still has extremely high nutrient loading, which appears to not have much adverse impact. Since the biogeochemistry of the estuary has been relatively similar for the past two decades, our multiple year research database is used in this review paper to address broad spatial and seasonal patterns of conditions in the tidal river and 120 km long saline bay. Dissolved oxygen concentrations show impact from allochthonous urban inputs and meteorological forcing as well as biological influences. Nutrient concentrations, although high, do not stimulate excessive algal biomass due to light and multiple nutrient element limitations. Since the bay does not have strong persistent summer stratification, there is little potential for bottom water hypoxia. Elevated chlorophyll concentrations do not exert much influence on light attenuation since resuspended bottom inorganic sediments dominate the turbidity. Dissolved inorganic carbon and dissolved and particulate organic carbon distributions show significant variability from watershed inputs and lesser impact from urban inputs and biological processes. Ratios of dissolved and particulate carbon, nitrogen, and phosphorus help to understand watershed and urban inputs as well as autochthonous biological influences. Owing to the relatively simple geometry of the system and localized anthropogenic inputs as well as a broad spatial and seasonal database, it is possible to develop these biogeochemical trends and correlations for the Delaware Estuary. We suggest that this biogeochemical perspective allows a revised evaluation of estuarine eutrophication that should have generic value for understanding other estuarine and coastal waters.     

大气污染物向海洋的输入及其生态环境效应

纵观20年来，特别是近几年来逐渐成为生物地球化学循环研究热点之一的大气对海洋物质输入的研究，从大气物质入海通量，大气物质入海对海洋生态系统和环境的影响，大气物质入海的科学研究计划和项目等方面分析了这一领域的研究现状和未来趋势。给出了不同海区各种主要大气入海物质的通量或在同类物质入海总量中的比例，讨论了氮、磷、铁等营养物质和持续性有毒污染物，如PAH、PCBs、杀虫剂和重金属对海洋生态系统和环境的不同影响。     

Characteristics of dissolved organic nitrogen (DON) in the surface water of Beijing Olympic Forest Park

The characteristics of dissolved organic nitrogen (DON) in surface water from Beijing Olympic Forest Park (BOFP) were investigated in this study. Nanofiltration (NF) pretreatment procedure using two NF membranes (NF90 and NF270) was applied to increase the accuracy and precision of DON measurements in surface water samples with high dissolved inorganic nitrogen/total dissolved nitrogen (DIN/TDN) ratios. Compared to NF90, NF270 showed better performance in lowering the DIN/TDN ratio and retaining DOC in both the synthetic water and raw water samples. DON concentrations ranged from 0.01 to 0.83 mg N L^?1 in water samples collected over four different months and showed a seasonal variation. The DON increased in summer due to the higher activity of decomposers on recent litterfall or because of a higher production of biomass in the surface water body. The molecular weight (MW) fractions of <3 kDa accounted for more than 50 % of the total DOC concentration and the fractions of <3 kDa contributed to more than 48 % of the total DON concentration. It could be concluded that most of the DON present in surface water of BOFP was composed of small molecules, which were mainly composed of monomers such as amino acids and urea, readily available for the uptake by phytoplankton and heterotrophic bacteria.     

The Contribution of Groundwater Discharge to Nutrient Exports from a Coastal Catchment: Post-Flood Seepage Increases Estuarine N/P Ratios

Four months of daily nutrient and radon (a natural groundwater tracer) observations at the outlet of a heavily drained coastal wetland illustrated how episodic floods and diffuse groundwater seepage influence the biogeochemistry of a sub-tropical estuary (Richmond River, New South Wales, Australia). Our observations downstream of the Tuckean Swamp (an acid sulphate soil floodplain) covered a dry stage, a flood triggered by a 213-mm rain event and a post-flood stage when surface water chemistry was dominated by groundwater discharge. Significant correlations were found between radon and ammonium and N/P ratios and between radon and dissolved organic nitrogen (DON) during the post-flood stage. While the flood lasted for 14?% of the time of the surface water time series, it accounted for 18?% of NH₄, 32?% of NO _x , 66?% of DON, 58?% of PO₄ and 55?% of dissolved organic phosphorus (DOP) catchment exports. Over the 4-month study period, groundwater fluxes of 35.0, 3.6, 36.3, 0.5 and 0.7?mmol?m^?2?day^?1 for NH₄, NO _x , DON, PO₄ and DOP, respectively, were estimated. The groundwater contribution to the total surface water catchment exports was nearly 100?% for ammonium, and <20?% for the other nutrients. Post-flood groundwater seepage shifted the system from a DON to a dissolved inorganic N-dominated system and doubled N/P ratios in surface waters. We hypothesise that the Richmond River Estuary N/P ratios may reflect a widespread trend of tidal rivers and estuaries becoming more groundwater-dominated and phosphorus-limited as coastal wetlands are drained for agriculture, grazing and development.     

Surface Water Metabolism Potential in Groundwater-Fed Coastal Waters of Hawaii Island,USA

Submarine groundwater discharge (SGD) has become increasingly recognized as an important source of freshwater and nutrients to coastal waters worldwide. Although groundwater nutrients have been found to cause algal blooms in many temperate coastal waters, little is known about the biological response to these nutrients in the tropics. On the leeward coast of Hawaii Island, SGD is the dominant freshwater and nutrient source to coastal waters. Kiholo Bay, HI and Kaloko-Honokohau National Historical Park, HI are two nearshore regions with well-documented SGD with high nutrient concentrations; however, little is known about how biological processes within the surface waters respond to these inputs. This study examined how potential gross primary production (pGPP), respiration (RESP), and potential metabolism (pMET) within surface waters differed inside and outside of groundwater plumes at these two sites and between wet and dry seasons. pGPP and RESP were both significantly higher within groundwater plumes, suggesting that SGD stimulated these biological processes; however, RESP responded to a much greater extent than pGPP, resulting in heterotrophic surface waters. RESP also varied seasonally, with greater rates during the dry season compared to the wet one; pGPP did not vary seasonally. Autotrophic conditions were found within groundwater plumes at Kiholo Bay, while heterotrophic conditions were found within them at Kaloko-Honokohau and were greater during the dry season. Overall, our results show that coastal biological processes respond to SGD and that their responses vary over short spatial and temporal scales.     

Radium-based pore water fluxes of silica, alkalinity, manganese, DOC, and uranium: A decade of studies in the German Wadden Sea

A decade of studies of metal and nutrient inputs to the back-barrier area of Spiekeroog Island, NW German Wadden Sea, have concluded that pore water discharge provides a significant source of the enrichments of many components measured in the tidal channels during low tide. In this paper we add studies of radium isotopes to help quantify fluxes into and out of this system. Activities of radium isotopes in surface water from tidal channels in the back-barrier area exhibit pronounced changes in concert with the tide, with highest activities occurring near low tide. Other dissolved components: silica, total alkalinity (TA), manganese, and dissolved organic carbon (DOC) exhibit similar changes, with patterns matching the Ra isotopes. Uranium follows a reverse pattern with highest concentrations at high tide. Here we use radium isotope measurements in water column and pore water samples to estimate the fluxes of pore waters that enter the tidal channels during low tide. Using a flushing time of 4 days and the average activities of ²²⁴Ra, ²²³Ra, and ²²⁸Ra measured in the back-barrier surface and pore waters, we construct a balance of these isotopes, which is sustained by a deep pore water flux of (2-4) × 10⁸ L per tidal cycle. This flux transports Ra and the other enriched components to the tidal channels and causes the observed low tide enrichments. An independent estimate of pore water recharge is based on the depletion of U in the tidal channels. The U-based recharge is about two times greater than the Ra-based discharge; however, other sinks of U could reduce the recharge estimate. The pore waters have wide ranges of enrichment in silica, alkalinity, manganese, DOC, and depletion of U with depth. We estimate concentrations of these components in pore water from the depth expected to contribute the majority of the pore water flux, 3.5 m, to determine fluxes of these components to the tidal channels. Samples from this depth have minimum concentrations of silica, alkalinity, manganese, and DOC. We also estimate the exports of these components (and import of U) due to mixing based on average measured concentrations in the tidal creeks and the 4-day flushing time. A comparison of these estimates reveals that the exports (negative in the case of U) equal or exceed the pore water fluxes. By using values slightly higher than the minimum concentrations at 3.5 m to calculate inputs, the two estimates could be forced to match. We conclude that pore water drainage is the major factor regulating fluxes of Ra isotopes, silica, alkalinity, manganese, DOC, and uranium in this system.     

Water Biogeochemistry of a Mangrove-Dominated Estuary Under a Semi-Arid Climate (New Caledonia)

Mangrove water biogeochemistry has been frequently studied under tropical climates, but less is known regarding mangroves in semi-arid climates. In this study, we examine the carbon and nutrient biogeochemistry in a mangrove tidal creek and in the main branch of a semi-arid estuary in New Caledonia. Porewater seepage represents a source of nutrients (DON, NH₄ ⁺, and DIP), carbon (DOC and CO₂), and alkalinity for the water column, but seawater dilution of the mangrove inputs is observed. Spatial and tidal variations in CO₂ fluxes along the tidal creek suggest that porewater seepage is a driver of CO₂ emission into the atmosphere. Large seasonal and spatial differences in the biogeochemical functioning of the main channel are observed and are mainly related to the seasonal rainfall pattern. During the rainy season, the watershed influences the entire estuary, which exhibits a typical positive circulation. During the dry season, the estuary turns into a salt-plug region with positive and negative circulations in the upper and lower reaches, respectively. In this case, the upper and lower reaches seem to function independently, and the biogeochemical functioning of their water column is not controlled by the same processes. Surprisingly, pCO₂@27 °C values tend to be higher during the dry season, as do the total alkalinity (TAlk) values, while the pH values exhibit an opposite trend. Moreover, the TAlk values are higher in the lower reaches during the wet season and in the upper reaches during the dry season. These results indicate high in situ biogeochemical reactions and high porewater influence during the dry season, likely because of a low flushing rate and high water residence time after salt plug establishment. Although our results suggest that salt plugs may significantly affect the water column’s biogeochemistry and may promote CO₂ emissions of mangrove-derived carbon, further investigations, especially mass balance studies, are required to quantify their role in the biogeochemical functioning of such estuarine systems.