Potential rates and environmental controls of denitrification and nitrous oxide production in a temperate urbanized estuary

Denitrification may play a major role in inorganic nitrogen removal from estuarine ecosystems, particularly in those subjected to increased nitrate and organic matter loads. The Douro estuary (NW Portugal) suffers from both problems: freshwater input of nitrate and organic load from untreated wastewater discharges. To assess how these factors might control sediment denitrification, a 12-month survey was designed. Denitrification potential and nitrous oxide (N₂O) production were measured at different locations using the slurry acetylene blockage technique. Denitrification rate ranged from 0.4 to 38 nmol N g⁻¹ h⁻¹, increasing towards the river mouth following an urban pollution gradient. N₂O production, a powerful greenhouse gas implicated on the destruction of the ozone layer, was significantly related with sediment organic matter and accounted for 0.5–47% of the N gases produced. Additional enrichment experiments were consistent with the results found in the environment, showing that sediments from the upper less urban stretch of the estuary, mostly sandy, respond positively to carbon and, inversely, in organic rich sediments from the lower estuary, the denitrification potential was limited by nitrate availability. The obtained results confirmed denitrification as an important process for the removal of nitrate in estuaries. The presence of wastewater discharges appears to stimulate nitrogen removal but also the production of N₂O, a powerful greenhouse gas, exacerbating the N₂O:N₂ ratio and thus should be controlled.     

Nitrous oxide production and denitrification rates in estuarine intertidal saltmarsh and managed realignment zones

Increasing concerns over habitat loss and rising costs of sea defence maintenance due to rising sea levels, has seen increases in the practice of managed realignment and reflooding of former reclaimed areas of intertidal saltmarsh and mudflat around the world. These practices are taking place with little knowledge of their impact on soil biogeochemical processes. Rates of denitrification (using the acetylene inhibition technique) and nitrous oxide (N₂O) production were measured from a long-established saltmarsh (SM) and an adjacent, recently re-flooded managed realignment (MR) site comprising former arable land in the estuary of the River Torridge, Devon, UK. Incubations were carried out in closed chambers in which patterns of tidal flooding were simulated automatically. Measurements were made during periods of flood and non-flood over a total of four tidal inundations with estuarine water. During the latter two flooding episodes floodwater was amended with nitrate (NO₃⁻). Nitrous oxide production in the SM soil generally was lower than in the MR soil, with mean values and standard errors over the whole incubation of 0.27 ± 0.16 mg N₂O-N m⁻² h⁻¹ and 0.65 ± 0.15 mg N₂O-N m⁻² h⁻¹ respectively. Denitrification rates demonstrated a similar trend although generally were an order of magnitude higher than N₂O production, with mean rates and standard errors of 2.88 ± 1.12 mg N₂O-N m⁻² h⁻¹ in the SM soil and 3.39 ± 1.16 mg N₂O-N m⁻² h⁻¹ in the MR soil. The data suggest that both soils are net sinks for NO₃⁻ and net sources for N₂O. Both patterns of tidal inundation and floodwater chemistry affect the process rates in each soil differently. The impact of flooding with NO₃⁻ – amended water was greater on the SM soil than the MR soil, and it is likely that decomposing vegetation buried in the accreting sediments following reflooding at the MR site were supplying a source of N in the soil, and so process rates were less dependent upon external supplies. The act of managed realignment in intertidal zones could therefore result in an increase in mean production of N₂O in intertidal zones, at least in the short term.     

Impact of trace metals on denitrification in estuarine sediments of the Douro River estuary,Portugal

Denitrification influences the nitrogen budget in estuaries by removing fixed nitrogen from the inorganic pool; rates are dependent on both geological and geographic conditions as well as increasing anthropogenic impacts. In this study the effects of copper (Cu), chromium (Cr), zinc (Zn), cadmium (Cd) and lead (Pb), on the denitrification pathway were evaluated in subtidal and intertidal sediments of the Douro River estuary. Dinitrogen, N₂O and NO₂⁻ production rates were measured in triplicate slurries of field samples under different treatments of metal concentrations. Results demonstrated that similar metal amendments led to different site responses for denitrification, suggesting that variations in sediment properties (metal concentrations, grain size, organic matter content, etc.) and/or differences in denitrifying community tolerance modulate the level of metal toxicity. Denitrifying communities in subtidal muddy sediments were not affected by increasing concentrations of metals. In contrast, intertidal sandy sites revealed high sensitivity to almost all trace metals tested; almost complete inhibition by Cr (95%) and Cu (85%) was observed for 98 and 79 μg per gram of wet sediment respectively, and by Zn (92%) at the highest concentration added (490 μg per gram of wet sediment). Moreover, the addition of trace metals stimulated N₂O and NO₂⁻ accumulation in intertidal sandy (Zn, Cu, Cr and Cd) and muddy sediments (Cu and Zn), demonstrating a pronounced inhibitory effect on specific steps within the denitrification enzymatic system. In summary, the results obtained suggest that, according to the type of estuarine sediment, trace metals cannot only reduce total N removal from an estuary via denitrification but also can enhance the release of N₂O, a powerful greenhouse gas.     

A role for nitrite in the production of nitrous oxide in the lower euphotic zone of the oligotrophic North Pacific Ocean

Understanding the role of the oceans in the Earth's changing climate requires comprehension of the relevant metabolic pathways which produce climatically important trace gases. The global ocean represents one of the largest natural sources of nitrous oxide (N₂O) that is produced by selected archaea and/or bacteria during nitrogen (N) metabolism. In this study, the role of nitrite (NO₂⁻) in the production of N₂O in the upper water column of the oligotrophic North Pacific Subtropical Gyre was investigated, focusing primarily on the lower euphotic zone where NO₂⁻ concentrations at the primary NO₂⁻ maximum reached 195 nmol L⁻¹. Free-drifting sediment trap arrays were deployed to measure N cycle processes in sinking particulate material and the addition of selected N substrates to unpreserved sediment traps provided an experimental framework to test hypotheses regarding N₂O production pathways and controls. Sinking particles collected using NO₂⁻-amended, unpreserved sediment traps exhibited significant production of N₂O at depths between 100 and 200 m. Subsequent stable isotope tracer measurements conducted on sediment trap material amended with ¹⁵NO₂⁻ yielded elevated δ¹⁵N values of N₂O, supporting N₂O production via a NO₂⁻ metabolism pathway. Experiments on seawater collected from 150 m showed N₂O production via NO₂⁻ metabolism also occurs in the water-column and indicated that the concentration of NO₂⁻ relative to NH₄⁺ availability may be an important control. These findings provide evidence for the production of N₂O via nitrifer-denitrification in the lower euphotic zone of the open ocean, whereby NO₂⁻ is reduced to N₂O by ammonia-oxidizing microorganisms.     

Spatio-temporal structure of diatom assemblages in a temperate estuary. A STATICO analysis

This study examines the spatio-temporal structure of diatom assemblages in a temperate estuary (Ria de Aveiro, Western Portugal). Eighteen monthly surveys were conducted, from January 2002 to June 2003, at three sampling sites (at both high and low tide) along the estuarine salinity gradient. The relationship of diatom assemblages and environmental variables was analysed using the STATICO method, which has been designed for the simultaneous analysis of paired ecological tables. This method allowed examination of the stable part of the environment-diatom relationship, and also the variations of this relationship through time. The interstructure factor map showed that the relationship between the 11 environmental variables and the abundance of the 231 diatom species considered was strongest in the months May and September 2002 and January, February and May 2003. The stable part of the species–environment relationships mainly consisted of a combined phosphate, chlorophyll a and salinity gradient linked to a freshwater-marine species gradient. A more pronounced gradient was observed in January, February and May 2003. Diatom assemblages showed clear longitudinal patterns due to the presence of both marine and freshwater components. May and September 2002 had the least structured gradients with marine-estuarine species appearing in the freshwater side of the gradient. The most complete gradient in February 2003 could be considered, in terms of bio-ecological categories, as the most structured period of the year, with a combination of strong marine influence in the lower zone and freshwater influence in the upper. The best-structured gradients were during periods of a diatom bloom. Stable diatom assemblages (with a strong structure and a good fit between the diatoms and environment) are described and characterized. This study shows the efficiency of the STATICO analysis. The inclusion of space-time data analysis tools in ecological studies may therefore improve the knowledge of the dynamics of species–environmental assemblages.     

Trophic structure and production in the macrobenthos of a temperate Australian estuary

The soft-bottom fauna of Gunnamatta Bay, Port Hacking, N.S.W., was sampled to estimate the abundance, trophic structure and net production of the macrobenthos. The samples were classified into groups from spatially distinct strata, the groups differing in species abundance and diversity and in the identity of the dominant species. The composition and community structure of the fauna was generally similar to that in other sheltered embayments on the southeastern coast of Australia. Estimated production values were low for an estuary, ranging from 10 kJ m^?2 year^?1 in an intertidal stratum of well sorted sand to 210–450 kJ m^?2 year^?1 in shallow subtidal strata with an admixture of silt. Estimated net production over all strata was 160 kJ m^?2 year^?1. Polychaetes dominated production, providing 45% of the total; crustaceans provided 20%, and molluscs and echinoderms 12% each. Detritus-feeders were dominant in most strata: the bivalve Theora fragilis, the polychaetes Australonereis ehlersi and Notomastus torquatus, and the urchin Echinocardium cordatum were major contributors to overall biomass and to net production. Substantial biomass and net production was also contributed by the suspension-feeding bivalve Corbula vicaria and a carnivorous crab Ceratoplax cf. glaberrimus. Overall, detritus-feeders contributed 61% of estimated net production, carnivores 32% and suspension-feeders 7%. Production estimated for carnivores was higher than could be supported by the non-carnivore populations, suggesting that some of the species considered to be carnivores have additional feeding modes. Excessive harvesting of bivalves by humans is suggested as the main reason for the low biomass of, and therefore low production by, suspension feeders.     

Mangrove (Avicennia marina subsp. australasica) litter production and decomposition in a temperate estuary

Mangrove forests can provide important cross-boundary subsidies of organic matter to adjacent habitats through the production, export, decomposition and assimilation of litter. We quantified two of these components in a temperate mangrove forest in Whangamata Harbour, New Zealand: 1) litter production; and 2) decomposition rates as a function of tidal elevation, sediment type and burial depth. Litter traps sampled monthly for a year measured an annual detrital input of 3.24–5.38 t DW ha^?1, of which 77% occurred in summer. Decomposition rates depended on litter type, with leaves decomposing faster (63 d to decay by 50%) than pneumatophore and wood material (316 and 460 d, respectively). Buried leaf and wood litter decomposed 1.3–1.4 times slower than litter on the sediment surface; however, tidal elevation and sediment type (mud vs. sand) had no effect. The slow decay of litter (an order of magnitude slower than tropical mangrove litter) suggests that its incorporation into temperate marine food webs may be relatively slow.     

曹妃甸近岸海域表层沉积物中重金属含量及潜在生态风险评价

文章对2014年9月曹妃甸近岸海域表层沉积物中重金属含量及其分布进行了分析,并利用Hankanson法对其潜在生态风险进行了评价。结果显示,曹妃甸近岸海域各调查站位沉积物中重金属含量均低于一类沉积物标准限值,Cd和Pb的平均含量均超过了渤海湾重金属背景值,沉积物中重金属含量随离岸距离的增加而呈降低趋势。重金属综合潜在生态风险指数RI为94.11,风险等级为中等,其中重金属潜在生态风险指数由大到小依次为Cd、Hg、Pb、Cu、Zn,除Cd以外其余重金属元素生态风险等级均为较低。重金属潜在生态风险随离岸距离的增加呈递减趋势,分析原因可能源于陆源污染。沉积物中重金属相关性分析表明:曹妃甸近岸海域沉积物中重金属元素Cd和Hg、Pb和Zn呈显著相关性,说明Cd、Hg、Pb、Zn可能具有相似来源。     

Distributions, sources and atmospheric fluxes of nitrous oxide in Jiaozhou Bay

The distributions, sources and atmospheric fluxes of nitrous oxide (N₂O) in the seawater of Jiaozhou Bay were investigated during four surveys in 2003 to evaluate this area as a source of N₂O to the atmosphere. N₂O concentrations in both the surface and bottom waters of Jiaozhou Bay showed obvious variability with both seasons and tidal cycles. Atmospheric fluxes of N₂O in Jiaozhou Bay showed seasonal and spatial variations, with the highest values occurring in summer and the lowest in winter. The annual emission of N₂O from the bay was estimated to be 1.09 × 10⁶–2.23 × 10⁶ mol yr⁻¹. N₂O in the water column of Jiaozhou Bay was found to come from several external sources including riverine water, sewage water and groundwater input, among which the riverine input was dominant while the groundwater input was rather limited. The spatial variation in distribution and atmospheric fluxes of N₂O in Jiaozhou Bay was influenced by the input of polluted river waters and sewage effluent along the eastern coast, which highlights the effects of human impacts on N₂O emission rates.     

闽江口放射性示踪沙实验的辐射安全分析和环境污染评价

本文报道了我们在应用放射性示踪沙观测闽江口底沙运动的实验过程中,同时进行的现场辐射剂量监测和实验区周围环境的放射性污染监测方法和结果,并进行了辐射安全分析和环境污染评价。     

南海东北部海水中N2O分布与产生机制的初步研究

2004年9月18—10月4日调查了南海东北部海水中氧化亚氮(N2O)浓度。表层海水中的N2O浓度平均值为8.40±0.79 nmol.L-1,饱和度平均为123%±11.6%,是大气N2O的源。不同区域表层海水中的N2O浓度存在明显差异,在水深200m层呈现南高、北低的分布特征。各层次海水中的N2O浓度均处于过饱和状态,N2O浓度由海水表层到底层呈上升趋势。ΔN2O与AOU间有显著的正线性相关性,说明海洋内部的硝化作用是产生N2O的主要机制。N2O的海-气通量平均值为0.72±0.36μmol.(m2.d)-1。     

春季东海溶存氧化亚氮的分布和海气交换通量

于2011年5至6月在东海采集不同深度海水样品,研究了其中溶存氧化亚氮(N2O)的分布并估算其海-气交换通量。结果表明,春季东海表层海水中溶存N2O浓度范围为6.31~11.88 nmol/L,平均值为(9.13±1.45)nmol/L;底层海水中N2O浓度范围为7.53~39.75 nmol/L,平均值为(13.71±7.76)nmol/L。随着深度的增加,N2O浓度逐渐升高。温度是影响春季东海N2O分布的主要因素,N2O浓度与温度呈负相关关系。长江冲淡水和黑潮水是东海N2O的重要来源。东海表层海水中N2O的饱和度范围为92.5%~139.3%,平均值为118.5%±10.3%,绝大多数站位都处于过饱和状态,因此,春季东海是大气N2O的净源。利用LM86公式和W92公式求得东海的海-气交换通量分别为(4.96±6.12)μmol/(m2·d)和(10.25±17.18)μmol/(m2·d),初步估算出东海年释放N2O通量约为0.061~0.127 Tg/a,占全球海洋释放总量的2.0%,远高于其所占的面积比0.2%。     

Physical and biological drivers of sediment oxygenation and denitrification in a New Zealand intermittently closed and open lake lagoon

Intermittently closed and open lakes and lagoons (ICOLLs) are shallow estuarine ecosystems, many of which show eutrophication symptoms. The physical and biological drivers of sediment oxygenation and denitrification were examined in a New Zealand ICOLL using in situ enclosures for one year. Denitrification was seasonally and spatially variable, and higher denitrification rates were driven by organic matter availability, temperature and nitrate flux. The bulldozing invertebrates generally deepened oxygen penetration in 18% of oxygen profiles, consistent with their effect in multiple regressions. Chironomid larvae (Chironomidae) dominated the benthic community, and their tubular burrows modified oxygen penetration into the sediment in 18% of profiles, potentially affecting denitrification in the ICOLL through bioirrigation. Our study shows that macroinvertebrates support increased sediment oxygenation; therefore the use of artificial opening regimes in many ICOLLs may have negative effects on macroinvertebrate community composition and may consequently inhibit denitrification.     

Longitudinal and depth variation of bacterioplankton productivity and related factors in a temperate estuary

Bacterioplankton productivity (BP) spatial variation was investigated in relation to potential resources, including primary productivity and dissolved organic matter, in the micro-tidal Neuse River–Pamlico Sound estuarine system, North Carolina, USA. Estuarine BP was predicted to correlate with the trophic gradient, decreasing along the salinity gradient in parallel with the decrease in organic matter and primary productivity. This prediction was tested over four years at spatial scales ranging from kilometers to meters along the riverine axis and with depth. The general pattern of BP across the salinity gradient was unimodal and matched the phytoplankton patterns in peak location and variability. Peak locations varied with discharge, especially in 2003 when above average discharge moved peaks downstream. Spatial coherence of BP with other variables was much less at short time scales. The effect of temperature, nutrients, and phytoplankton on BP varied by location, especially fresh versus brackish stations, although only temperature explained more than 20% of the BP variation. Depth variation of BP was as great as longitudinal variation and bottom samples were often higher than surface. BP was strongly correlated with particulate organic carbon at the pycnocline and bottom, highlighting the importance of particulate matter as a resource. Station-averaged BP and phytoplankton data corresponded well with two published meta-analyses, although the offset of the freshwater station suggested longitudinal differences in community composition or resource availability.     

Differences in nitrous oxide distribution patterns between the Bering Sea basin and Indian Sector of the Southern Ocean

Nitrous oxide （N2O） distribution patterns in the Bering Sea basin （BSB） and Indian Sector of the Southern Ocean （ISSO） were described and compared. In both sites, the waters were divided into four layers： surface layer, subsurface layer, N2O maximum layer, and deep water. Simulations were made to find out the most important factors that regulate the N2O distribution patterns in different layers of both sites. The results showed that in the surface water, N2O was more understaturated in the ISSO than the BSB. This phenom- enon in the surface water of ISSO may result from ice melt water intrusion and northeastward transport of the Antarctic surface water. Results of the rough estimation of air-sea fluxes during the expedition were （-0.34±0.07）-（-0.64±0.13） μmol/（m2·d） and （-1.47±0.42）-（-1.77±0.51） μmol/（m-2·d） for the BSB and the ISSO, respectively. Strongly stratified surface layer and temperature minimum layer restricted exchange across the thermocline. The N2O maximum existed in higher concentration and deeper in the BSB than the ISSO, but their contribution to the upper layer by eddy diffusions was negligible. In deep waters, a concentration difference of 5 nmol/L N2O between these two sites was found, which suggested that N2O production occurred during thermohaline circulation. N2O may be a useful tracer to study important large-scale hydrographic processes.     

Behaviour of boron,calcium and magnesium in a polluted estuary

Behaviour of industrially added boron in the well mixed Ambika river estuary of South Gujarat, India has been studied along with that of calcium and magnesium. The ratios of Ca : Cl and Mg : Cl at varying chlorinities were always within the normal ranges found in river water at one end and seawater at the other end. B : Cl exceeded the river water end limit at the ebb tide at an upstream station. Percentage addition or removal of boron, calcium and magnesium was calculated using the concept of the theoretical dilution line. The external input raised the boron concentration by 263% in the vicinity of the industrial discharge. A correlation coefficient of ?0·82 between chlorinity and percentage addition or removal of boron supports the theory of boron incorporation in sediments in amounts proportional to salinity. Inverse relationship between percentage addition or removal of boron and suspended solids was observed. Behaviour of calcium and magnesium was in line with the replacement of Ca²⁺ ions occupying the majority of ion-exchange sites in riverine clays by Mg²⁺, Na⁺ and K⁺ during their first encounter with seawater.     

Phosphorus speciation and availability in intertidal sediments of a temperate estuary: relation to eutrophication and annual P-fluxes

For a better understanding of the phosphorus dynamics and bioavailability in temperate climates, sequential chemical extraction techniques were used to study sediment P-pools distribution and relative importance in a eutrophicated estuary.Results indicate a shift in importance from the iron-bound P fraction to the CaCO₃-bound P fraction with increasing salinity, which suggests a decrease in bioavailable P from the most inner part of the estuary seaward, as the CaCO₃ associated P is believed to be less available for organisms. Salt marsh plants also influence sediment P speciation, through higher organic P fractions (mainly humic acid associated P) when compared to non-vegetated sediments. The ratio of iron-bound P to iron-oxyhydroxides may be used as an indicator of P availability, since it reflects the number of available P sorption sites in the metal oxides. This ratio was lowest in the intermediate zone of the estuary (13.7) when compared to the outer site (29.6) and the upper site (26.1), suggesting saturation of sorption sites. Co-incident with this, the intermediate site is characterized by the occurrence of macroalgal blooms during summer. In the present case, superficial sediments in the Mondego estuary do not show a clear seasonal trend, either in total amounts of exchangeable P or P speciation. Pools of exchangeable P in the surface sediment were 30 times higher than the annual net-export of P (14 ton year⁻¹) from the estuary. The annual P release from the sediment appears diminutive in comparison with the pool-size. Management measures to reduce nutrient input into coastal water systems should therefore consider that phosphorus availability may persist as a result of sediment supply, even after reducing the external point sources.     

Environmental cues and seasonal reproduction in a temperate estuary: a case study of Owenia collaris (Annelida: Polychaeta,Oweniidae)

Coordination of gametogenesis and spawning during restricted breeding seasons increases availability of mates, fertilization rates, and often success of offspring. Orton’s Rule predicts water temperature as the dominant environmental cue for gametogenesis or spawning in temperate invertebrates. Crisp’s Rule predicts that species producing planktotrophic larvae will time their reproduction to ensure optimal nutrition for the larvae. Owenia collaris (Annelida: Oweniidae) is a temperate polychaete that produces planktotrophic larvae that remain in the water column for several weeks. Reproductive phenology and its relationship to the environment were investigated in an estuarine population of O. collaris using field and laboratory studies. Owenia collaris produced mature gametes between March and September each year during the productive season between the spring and fall transitions when day lengths were 12 h or more, alkalinity was 8.1 or higher, and temperature was 11 °C or higher. Gamete production was not related to seasonal changes in salinity or benthic phytoplankton concentrations and gametes were present prior to the spring phytoplankton bloom. In laboratory experiments, production of gametes was influenced somewhat by manipulating day lengths but not adult food. The association with predictable and stable environmental cycles (day length) and a broad spawning season suggest that this species is unlikely to mis-match with larval food availability which would lead to reduced availability of recruits in any given year, supporting Crisp’s Rule. Our data do not support the hypothesis that reproductive timing in this species is driven by access to excess energy required by adults to initiate the production of gametes. Our data also do not support Orton’s premise that temperature is the primary controlling factor of reproduction in this temperate marine invertebrate.     

Assessment of spatial variation in carbon utilization by benthic and pelagic invertebrates in a temperate South African estuary using stable isotope signatures

Stable isotope analyses (δ¹³C and δ¹⁵N) were used to evaluate the spatial variations in carbon flow from primary producers to consumers at two sites in the temperate and permanently open Kariega Estuary on the southeastern coast of South Africa during October 2005 and February 2006. One site was located opposite a salt marsh while the second was upstream of the marsh. Except for significantly enriched δ¹³C values of Zostera capensis and surface sediments near the salt marsh, the δ¹³C and δ¹⁵N signatures of the producers were similar between sites. The invertebrates were clustered into groups roughly corresponding to the predominant feeding modes. The suspension feeders showed δ¹³C values closest to the seston, whereas the deposit feeders, detritivores and scavengers/predators had more enriched δ¹³C values reflecting primary carbon sources that were likely a combination of seston, Spartina maritima and Z. capensis at the upstream site, with an increased influence of benthic algae and Z. capensis at the salt marsh site. The δ¹⁵N signatures of the consumers showed a stepwise continuum rather than distinct levels of fractionation, indicating highly complex trophic linkages and significant dietary overlap among the species. Consumers exhibited significantly enriched δ¹³C values at the salt marsh site, an effect that was attributed to enriched Z. capensis detritus in this region in addition to increased phytoplankton biomass in their diets compared with invertebrates living upstream. The data reinforce the concept that between-site variations in the stable isotope ratios of consumers can result not only from dietary shifts, but also from alterations in the isotope ratios of primary producers.