用镭同位素评价海水滞留时间及海底地下水排泄

海底地下水排泄(submarine groundwater discharge, SGD)难以直接测量, 镭同位素和氡-222等天然示踪剂使得间接评价SGD通量成为可能.为了评价五缘湾的水体滞留时间和SGD通量, 实测了湾内海水、湾外海水和地下水中224Ra和226Ra的活度, 利用224Ra和226Ra半衰期的差异, 采用224Ra与226Ra的活度比值计算湾内水团的年龄和平均滞留时间, 利用224Ra和226Ra的质量平衡模型计算SGD通量.五缘湾13个站位的水团年龄在0.6~2.4 d之间, 湾顶水团年龄相对较大, 平均海水滞留时间1.4 d.地下水输入五缘湾的224Ra和226Ra通量分别为5.17×106 Bq/d和5.28×106 Bq/d, 将该通量用地下水端元的活度转换成为SGD通量分别是0.21 m3/m2/d(224Ra平衡模型)和0.23 m3/m2/d(226Ra平衡模型), 两种模型的结果较接近, 其平均值0.22 m3/m2/d可作为五缘湾的海底地下水排泄通量.      

镭同位素示踪盐湖地下水排放通量——以大柴旦盐湖为例

为了解大柴旦盐湖地下水排放通量,测试了深部热水、浅层地下水、河流水、盐湖表层水中镭同位素(223 Ra、224 Ra、226 Ra和228 Ra)的活度值.研究结果表明湖水中223 Ra、224 Ra、226 Ra和228 Ra的活度值,在盐度较低时随着盐度的增加而升高,当盐度大于168.99‰时,则随着盐度的增加而降低,这是由于在靠近河口区湖中镭同位素先发生解吸,蒸发后期湖中镭同位素发生了共沉淀的原因.223 Ra、224 Ra和228 Ra的活度值在深部地下热水比在自然露头热水中高;而226 Ra正好相反,自然露头地下热水中226 Ra具有明显的积累现象.丰水期深部地下热水、浅层地下水和河流三个端元对大柴旦湖中镭同位素贡献比例分别为0.01、0.31和0.68.水体平均停留时间是9.13 d.由深部地下热水排放到大柴旦的通量变化范围为1.17×103±2.02～1.31×103±10.17 m3/d,平均为1.24×103±12.20 m3/d,浅层地下水排放通量变化范围为1.58×106±4.92×103～2.61×106±2.71×104m3/d,平均为2.09×106±3.20×104m3/d.本研究将为盐湖中地下水排放示踪提供一种有效的方法.     

咸水环境下沉积物中镭的解吸特点

海底沉积物向上覆水体扩散的镭是海洋水体中镭同位素的重要来源之一。为了研究沉积物中镭同位素的解吸和扩散特点,进行了不同盐度和不同粒度条件下224Ra和226Ra解吸的模拟实验,并通过多个时间段的沉积物培养实验获取224Ra和226Ra的扩散通量。实验结果表明:随着水体盐度增大,沉积物中224Ra、226Ra的解吸量随之增加,在盐度为25时,解吸量基本达到最大值;在同一咸水环境条件下,4个粒级(2000~1000μm、1000~500μm、500~250μm、250~125μm)的沉积物的224Ra、226Ra解吸量比较接近,粒级2000μm的224Ra、226Ra解吸量略高于上述4个粒级,而粒级125μm的224Ra、226Ra解吸量远大于上述5个粒级;胶州湾沉积物中224Ra和226Ra的平均扩散通量分别为0.85 Bq·m–2·d–1和0.022 Bq·m–2·d–1。     

闽江河口区水体中镭的分布特征及河水与海水的混合速率

入海河口中河水与海水的混合是海洋学中一个重要的界面过程,两者混合尺度和混合速率关系到河流携带物质的扩散范围和归宿,采用天然示踪剂²²⁴Ra和²²⁶Ra计算河水与海水的混合速率。2010年8月28日,采集了闽江河口区地下水样20个、河水样13个、河水与海水的混合水样12个,分别测量了每个水样的盐度、²²⁴Ra活度和²²⁶Ra活度。结果表明：地下水中²²⁴Ra、²²⁶Ra活度普遍高于河水;所有水体中的²²⁴Ra活度普遍都高于²²⁶Ra活度;河水遇到海水后,²²⁴Ra活度出现较大幅度的增加,而²²⁶Ra活度的增加并不明显。基于²²⁴Ra与²²⁶Ra半衰期的差异,在只有河水与海水发生涡流混合的情况下,计算获得河水与海水的混合速率为140.2~142.5 m/h。     

用镭同位素评价九龙江河口区的地下水输入

为评价九龙江河口区的地下水输入量及其输送的营养盐数量,建立了天然存在的镭同位素224Ra和226Ra的质量平衡模型。镭的源项考虑了河流的输入、河流悬浮颗粒的解吸、沉积物再悬浮颗粒的解吸、沉积物扩散输入、涨潮时外海的输入和地下水的输入;镭的汇项考虑了镭的放射性衰变,以及退潮时河口水的输出。根据镭的质量平衡计算,地下水输入的镭通量约占河口区镭总输入通量的41.9%~56.9%,转换成地下水输入量为1.65亿1.83亿m3/d,该地下水输入量是河流径流输入量的4倍多。以陆源地下淡水占总的地下水输入量的10%考虑,计算获得营养盐输入通量分别为461万mol/d(DIN)、22万mol/d(DIP)、694万mol/d(DSi),它们分别约是河流输入营养盐通量的23%(DIN)、28%(DIP)、77%(DSi)。结果表明九龙江河口的地下水输入量及其所输送的营养盐相当可观,所输入的营养盐是海域富营养化的潜在影响因素,在未来的河口环境管理中应引起重视。     

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。     

近岸海域^226Ra的时空变化与海底地下水排泄（SGD）估算

海底地下水排泄（submarine groundwater dischurge,SGD）是沿海地区陆地物质向海洋输送的重要途径,中国具有漫长的海岸线．准确地评估我国沿海地区的SGD及其对沿海海洋生态环境的潜在影响具有重要的理论与实践意义。本文以浙江舟山朱家尖海湾为研究区域,通过冬、夏两季地下水和海水的同步采样分析,在研究地下水和海水中镭（^226Ra）时空变化的基础上,利用^226Ra的质量平衡原理,估算了研究区内SGD的通量为240×10^5～230×10^6m^3／d,根据12月份枯水期推算的全年保守通量为864×10^7～828×10^8m^3／a,另外,根据年平均降水量等水文参数估算的氮、磷和硅营养盐年平均的入海通量分别为3.256t／a、0.029t／a和52.775t／a。     

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。     

基于~(222)Rn质量平衡模型的胶州湾海底地下水排泄

海底地下水排泄(SGD)作为全球水循环的一个组成部分,近年来成为陆海相互作用的研究热点。地球化学示踪法是研究海底地下水排泄的主要手段。本文以环境同位素222Rn作为示踪剂,通过构建222Rn质量平衡模型来评价胶州湾的海底地下水排泄,并进一步估算地下水输入的营养盐。222Rn质量平衡模型的源项考虑了河流的输入、沉积物的扩散、母体226Ra的支持,汇项考虑了222Rn的自身衰变、222Rn散逸到大气的损失以及与湾外海水的混合损失,源汇项的差值则作为地下水输入的222Rn通量。结果表明,2011年9—10月胶州湾海底地下水排泄通量为24.2 L?m–2?d–1,2012年4—5月胶州湾海底地下水排泄通量为7.8 L?m–2?d–1。丰水季节地下水输入胶州湾的营养盐低于河流输入的,但是枯水季节地下水输入的营养盐接近河流输入的,特别是输入的活性磷酸盐和硅酸盐很接近。     

全球海水剖面Fe同位素组成的不均一性及其影响因素

全球海水剖面Fe同位素组成存在显著不均一性.对大西洋洋中脊、大西洋近海岸带、东太平洋和西太平洋弧后扩张中心多个站位的海水剖面溶解Fe浓度和Fe同位素组成进行了综合分析,得出以下主要认识:（1）不同区域的海水剖面溶解Fe浓度和Fe同位素组成呈现不同的变化特征,海水Fe同位素的变化趋势与海水溶解氧浓度变化一致,而与海水溶解Fe浓度呈镜像变化关系;（2）不同深度的海水溶解Fe浓度和Fe同位素组成特征的主要控制因素不同.表层海水受到大气降尘、生物作用影响呈现富重Fe同位素特征,受河流的影响Fe同位素组成偏轻;深层海水主要受到深海沉积和海底热液活动的影响,其中沉积物中的非还原溶解Fe导致海水富集重Fe同位素,而受洋中脊热液流体影响的深部海水显著富集轻Fe同位素;（3）将目前已知海底热液溶解Fe通量最小值（0.5 Gmol/a）作为全球大洋的热液溶解Fe通量,利用不同来源的溶解Fe同位素与其通量间的关系估算海底热液对海洋的Fe循环的贡献为~5.5%.由于海底热液流体的Fe通量可能远大于0.5 Gmol/a,因此,海底热液活动对海洋溶解Fe的贡献可能远超过前人的估算结果（6.0%）.      

Application of226Ra,228Ra,223Ra, and224Ra in coastal waters to assessing coastal mixing rates and groundwater discharge to oceans

The fate of dissolved material delivered to the coastal ocean depends on its reactivity and the rate at which it is mixed offshore. To measure the rate of exchange of coastal waters, we employ two short-lived radium isotopes,²²³Ra and²²⁴Ra. Along the coast of South Carolina, shore-perpendicular profiles of²²³Ra and²²⁴Ra in surface waters show consistent gradients which may be modeled to yield eddy diffusion coefficients of 350–540 m²s⁻¹. Coupling the exchange rate with offshore concentration gradients yields estimates of offshore fluxes of dissolved materials. For systems in steady state, the offshore fluxes must be balanced by new inputs from rivers, groundwater, sewers or other sources. Two tracers that show promise in evaluating groundwater input are barium and²²⁶Ra. These tracers have high relative concentrations in the fluids and low-reactivity in the coastal ocean. Applying the eddy diffusion coefficients to the offshore gradient of²²⁶Ra concentration provides an estimate of the offshore flux of²²⁶Ra. Measuring the concentrations of²²⁶Ra in subsurface fluids provides an estimate of the fluid flux necessary to provide the²²⁶Ra. These estimates indicate that the volume of groundwater required to support these fluxes is of the order of 40% of the surface water flow.     

Variations of Hydrodynamics and Submarine Groundwater Discharge in the Yellow River Estuary Under the Influence of the Water-Sediment Regulation Scheme

The “Water-Sediment Regulation Scheme” (WSRS) is critically important to the hydrologic evaluation of the Yellow River estuary since a huge pulse of water and sediment are delivered into the sea during a short period. We used the natural geochemical tracers radium (²²³Ra, ²²⁴Ra, ²²⁶Ra) and radon (²²²Rn) isotopes as well as other hydrological parameters to investigate the mixing variations and submarine groundwater discharge (SGD) in the Yellow River estuary under the influence of the 2013 WSRS. Dramatically elevated radium and radon isotopic activities were observed during this WSRS compared with activities measured during a non-WSRS period. Radium “water ages” indicated that the offshore transport rate nearly tripled when the river discharge increased from 400 to 3400 m³/s. We calculated the SGD flux in the Yellow River estuary based on a radium mass balance model as well as radium and radon time-series models. The SGD flux was estimated at 0.02~0.20 m/day during a non-WSRS period and 0.67~1.22 m/day during the 2013 WSRS period. The results also indicate that large river discharge tends to lead more intense SGD along the river channel direction with a large amount of fresh SGD.     

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.     

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.     

Submarine groundwater discharge in a subsiding coastal lowland: A Ra and Rn investigation in the Southern Venice lagoon

Several recent studies have suggested that submarine groundwater discharge (SGD) occurs in the Venice lagoon with discharge rates on the same order or larger than the surface runoff, as demonstrated previously in several other coastal zones around the world. Here, the first set of ²²²Rn data, along with new ²²⁶Ra data are reported, in order to investigate the occurrence and magnitude of SGD specifically in the southern basin of the lagoon. The independent connection with the Adriatic Sea (at the Chioggia inlet), in addition to the relative isolation of the water body from the main lagoon, make this area an interesting case study. There is probably only minimal fresh groundwater flux to the lagoon because the surrounding aquifer is subsiding and mainly has a lower hydraulic head than seawater.The data show that the Ra and Rn activities are in slight excess in the lagoon compared to the open sea, with values on the same order as those observed in the northern and central basins. Taking into account the water exchange rate between the lagoon and adjacent seawater provided by previous hydrodynamic numerical modelling, it is shown that this excess cannot be supported at steady state by only riverine input and by diffusive release from the sediment interstitial water. High activities observed in groundwater samples collected from 16 piezometers tapping into the shallow aquifer over the coastal lowland substantiate that the excess radioactivity in the lagoon may indeed be due to the advection of groundwater directly into the lagoon bottom water through the sediment interface. However, the data show that the groundwater composition is extremely heterogeneous, with high Ra activities concentrated within a narrow coastal strip where the contact between fresh and saline water takes place, while Rn strongly decreases when approaching the lagoon shore across the 20 km coastal plain. Assuming that the average groundwater activities measured in the coastal strip are representative of the SGD composition, a SGD flux of 7.7 ± 3.5 × 10⁵ and 2.5 ± 2 × 10⁶ m³/d is calculated using a ²²⁶Ra and ²²²Rn budget, respectively, (i.e. about 1-3 times the surface runoff), substantially lower than in previous studies. The influence of all assumptions on SGD estimates (groundwater heterogeneity, diffusive sediment flux, one-box versus multi-boxes model calculations) is discussed, and a sensitivity analysis of the influence of imperfect exchange and mixing at the lagoon outlets that affects the lagoon composition is provided. Finally, the results confirm that the SGD flux, calculated with these assumptions, is largely (∼80%) composed of saline lagoon water circulating through the sediment under the lagoon margin, and that the fresh water discharge associated with SGD is at most a minor term in the lagoon hydrologic balance.     

A multi-method approach for groundwater resource assessment in coastal carbonate (karst) aquifers: the case study of Sierra Almijara (southern Spain)

Understanding the transference of water resources within hydrogeological systems, particularly in coastal aquifers, in which groundwater discharge may occur through multiple pathways (through springs, into rivers and streams, towards the sea, etc.), is crucial for sustainable groundwater use. This research aims to demonstrate the usefulness of the application of conventional recharge assessment methods coupled to isotopic techniques for accurately quantifying the hydrogeological balance and submarine groundwater discharge (SGD) from coastal carbonate aquifers. Sierra Almijara (Southern Spain), a carbonate aquifer formed of Triassic marbles, is considered as representative of Mediterranean coastal karst formations. The use of a multi-method approach has permitted the computation of a wide range of groundwater infiltration rates (17–60%) by means of direct application of hydrometeorological methods (Thornthwaite and Kessler) and spatially distributed information (modified APLIS method). A spatially weighted recharge rate of 42% results from the most coherent information on physiographic and hydrogeological characteristics of the studied system. Natural aquifer discharge and groundwater abstraction have been volumetrically quantified, based on flow and water-level data, while the relevance of SGD was estimated from the spatial analysis of salinity, ²²²Rn and the short-lived radium isotope ²²⁴Ra in coastal seawater. The total mean aquifer discharge (44.9–45.9 hm³ year^?1) is in agreement with the average recharged groundwater (44.7 hm³ year^?1), given that the system is volumetrically equilibrated during the study period. Besides the groundwater resources assessment, the methodological aspects of this research may be interesting for groundwater management and protection strategies in coastal areas, particularly karst environments.