Investigating Bermuda's pollution history through stable isotope analyses of modern and museum-held gorgonian corals

For centuries, Bermuda has been challenged with wastewater management for the protection of human and environmental health. By quantifying the δ¹⁵N of the common sea fan Gorgonia ventalina sampled from 30 sites throughout Bermuda we show that sewage-derived nitrogen is detectable on nearshore coral reefs and declines across the lagoon to the outer rim. We also sampled gorgonians from two museum collections representing a 50y time-series (1958–2008). These samples revealed an increase in δ¹⁵N of > 4.0‰ until the mid-1970s, after which δ¹⁵N values slowly declined by ~ 2.0‰. A δ¹⁵N chronology from a gorgonian skeleton exhibited a similar decline over the last 30–40 years of approximately 0.6‰. We conclude that policies have been effective in reducing sewage impacts to Bermudian reefs. However, significant sources of sewage pollution persist and are likely have a strong impact on harbor and nearshore coral communities and human health.     

Using a macroalgal δ15N bioassay to detect cruise ship waste water effluent inputs

Green macroalgae bioassays were used to determine if the δ¹⁵N signature of cruise ship waste water effluent (CSWWE) could be detected in a small harbor. Opportunistic green macroalgae (Ulva spp.) were collected, cultured under nutrient depleted conditions and characterized with regard to N content and δ¹⁵N. Samples of algae were used in controlled incubations to evaluate the direction of isotope shift from exposure to CSWWE. Algae samples exposed to CSWWE exhibited an increase of 1-2.5‰ in δ¹⁵N values indicating that the CSWWE had an enriched isotope signature. In contrast, algae samples exposed to field conditions exhibited a significant decrease in the observed δ¹⁵N indicating that a light N source was used. Isotopically light, riverine nitrogen derived from N₂-fixing trees in the watershed may be a N source utilized by algae. These experiments indicate that the δ¹⁵N CSWWE signature was not detectable under the CSWWE loading conditions of this experiment.     

Variation in diet across an elevational gradient in the larvae of two Hydropsyche species (Trichoptera)

While specialized species are linked to a particular resource, omnivorous species may switch between food items according to the availability and the quality of resources. Here we use larvae of the omnivorous caddisfly genus Hydropsyche (Trichoptera) to analyse changes in diet composition across an elevational gradient. Periphyton and Hydropsyche larvae were sampled from 22 populations at stream orders from 2 to 5 on the German part of the Bohemian Forest. Elevations of sampling sites ranged between 300 m and 900 m a.s.l.. Diet composition was estimated by the analyses of the gut content of larvae as well as by stable nitrogen isotopes (δ¹⁵N). The δ¹⁵N values of the periphyton decreased and the C/N ratio of periphyton increased with increasing environmental harshness (decreasing water pH, temperature and conductivity with increasing elevation) indicating a decrease of periphyton food quality. Across individuals, the proportion of animals in the gut of Hydropsyche larvae was positively related to the difference of δ¹⁵N values between larvae and periphyton. The proportion of animals within the gut and (baseline corrected) δ¹⁵N values of Hydropsyche populations increased with increasing environmental harshness. We suggest that the (i) low primary production caused by shading, low temperatures and low nutrient levels, (ii) the low nutrient quality of periphyton and (iii) the availability of animal prey due to the input of allochthonous resources in headwaters caused the shift in the diet of Hydropsyche larvae along the river continuum.     

δ15N variation in Ulva lactuca as a proxy for anthropogenic nitrogen inputs in coastal areas of Gulf of Gaeta (Mediterranean Sea)

We tested the capacity of Ulva lactuca to mark N sources across large marine areas by measuring variation in its δ¹⁵N at several sites in the Gulf of Gaeta. Comparisons were made with the macroalga Cystoseira amentacea. Variation of δ¹⁵N values was assessed also in the coastal waters off the Circeo Natural Park, where U. lactuca and C. amentacea were harvested, as these waters are barely influenced by human activities and were used as reference site. A small fragment from each frond was preserved before deployment in order to characterize the initial isotopic values. After 48 h of submersion, U. lactuca was more responsive than C. amentacea to environmental variation and δ¹⁵N enrichment in the Gulf of Gaeta was observed. The spatial distribution of δ¹⁵N enrichment indicated that different macro-areas in the Gulf were affected by N inputs from different origins. Comparison of the δ¹⁵N values of fragments taken from the same transplanted frond avoided bias arising from natural isotopic variability.     

Ballast water as a vector of coral pathogens in the Gulf of Mexico: the case of the Cayo Arcas coral reef

The discharge of nutrients, phytoplankton and pathogenic bacteria through ballast water may threaten the Cayo Arcas reef system. To assess this threat, the quality of ballast water and presence of coral reef pathogenic bacteria in 30 oil tankers loaded at the PEMEX Cayo Arcas crude oil terminal were determined. The water transported in the ships originated from coastal, oceanic or riverine regions. Statistical associations among quality parameters and bacteria were tested using redundancy analysis (RDA). In contrast with coastal or oceanic water, the riverine water had high concentrations of coliforms, including Vibrio cholerae 01 and, Serratia marcescens and Sphingomona spp., which are frequently associated with “white pox” and “white plague type II” coral diseases. There were also high nutrient concentrations and low water quality index values (WQI and TRIX). The presence of V. cholerae 01 highlights the need for testing ballast water coming from endemic regions into Mexican ports.     

Nitrogen cycling in the German Bight (SE North Sea) — Clues from modelling stable nitrogen isotopes

Nitrogen isotope values (δ¹⁵N) of surface sediments in the German Bight of the North Sea exhibit a significant gradient from values of 5–6‰ of the open shelf sea to values above 11‰ in the German Bight. This signal has been attributed to high reactive N (N_r) loading enriched in ¹⁵N from rivers and the atmosphere. To better understand the processes that determine the intensity and spatial distribution of δ¹⁵N anomalies in surface sediments, and to explore their usefulness for reconstructions of pristine N-input from rivers, we modeled the cycling of the stable isotopes ¹⁴N and ¹⁵N in reactive nitrogen through the ecosystem of the central and southern North Sea (50.9–57.3°N, 3.4°W−9.2°E) for the year 1995. The 3D-ecosystem model ECOHAM amended with an isotope-tracking module was validated by δ¹⁵N data of surface sediments within the model domain. A typical marine value (δ¹⁵N_nitrate=5‰) was prescribed for nitrate advected into the model domain at the seaside boundaries, whereas δ¹⁵N_nitrate of river inputs were those measured bi-monthly over 1 year; δ¹⁵N values of atmospheric deposition were set to 6‰ and 7‰ for NO_x and NH_y, respectively. The simulated δ¹⁵N values of different nitrogen compounds in the German Bight strongly depend on the mass transfers in the ecosystem. These fluxes, summarized in a nitrogen budget for 1995, give an estimate of the impacts of hydrodynamical and hydrological boundary conditions, and internal biogeochemical transformations on the nitrogen budget of the bight.     

Macroalgae blooms and δN in subtropical coastal lagoons from the Southeastern Gulf of California: Discrimination among agricultural, shrimp farm and sewage effluents

Macroalgae blooms of Gracilaria vermiculophylla, Hypnea spinella and Spyridia filamentosa have been found in coastal lagoons in the SE Gulf of California. Agriculture, livestock, shrimp and poultry farms and sewage contribute anthropogenic nitrogen to the systems. The δ¹⁵N of these sources, water column and macroalgae were studied in order to identify the N supply for macroalgae blooms. δ¹⁵N of three species of macroalgae (4.3-13.6‰) were enriched compared to the water column ( 3.7-6.8‰), probably because of fractioning from the macroalgae. δ¹⁵N of POM (1.4-10.3‰) was similar to the water column but the relationship was unclear. Depending on the site, macroalgae showed different δ¹⁵N values since some sites receive more or less influence from one given source of the associated watershed, which is reflected in the different δ¹⁵N values of the macroalgae of the same system and in the relative contributions of the sources.     

Are seagrass beds indicators of anthropogenic nutrient stress in the rocky intertidal?

It is well established that anthropogenic nutrient inputs harm estuarine seagrasses, but the influence of nutrients in rocky intertidal ecosystems is less clear. In this study, we investigated the effect of anthropogenic nutrient loading on Phyllospadix spp., a rocky intertidal seagrass, at local and regional scales. At sites along California, Washington, and Oregon, we demonstrated a significant, negative correlation of urban development and Phyllospadix bed thickness. These results were echoed locally along an urban gradient on the central California coast, where Phyllospadix shoot δ¹⁵N was negatively associated with Phyllospadix bed thickness, and experimentally, where nutrient additions in mesocosms reduced Phyllospadix shoot formation and increased epiphytic cover on Phyllospadix shoots. These findings provide evidence that coastal development can threaten rocky intertidal seagrasses through increased epiphytism. Considering that seagrasses provide vital ecosystem services, mitigating eutrophication and other factors associated with development in the rocky intertidal coastal zone should be a management priority.     

Spatial distributions of δ13C, δ15N and C/N ratios in suspended particulate organic matter of a bay under serious anthropogenic influences: Daya Bay,China

Stable isotopic signatures (δ¹³C and δ¹⁵N) and C/N ratios of suspended particulate organic matter (POM) were investigated from the surface water of Daya Bay during summer and winter of 2015. The relatively high δ¹³C_POM values suggested the input of ¹³C-depleted terrigenous organic matter was low in Daya Bay. There were significant correlations between δ¹³C_POM values and chlorophyll a concentrations both during summer and winter, suggesting the δ¹³C_POM values were mainly controlled by the phytoplankton biomass in the surface water. The distribution of δ¹⁵N_POM values was more complicated than that of δ¹³C_POM and displayed low values in the outer bay and the Dan'ao River estuary. ¹⁵N-depleted ammonia originating from industrial wastewater might have strongly influenced the water quality and stable isotopic signatures of POM near the Dan'ao River estuary. The δ¹³C_POM and δ¹⁵N_POM values strongly reflect the influences of anthropogenic activity and eutrophication in Daya Bay.     

Interannual changes in δN values in Fucus vesiculosus L.

The natural abundance of ¹⁵N (δ¹⁵N) has been widely used to detect anthropogenically derived N loads in environmental impact studies. The present study involved retrospective analysis of subsamples of Fucus vesiculosus L. collected during a period of three years (2008–2010) from two sites: a control site, within a coastal reference area, and an area affected by the effluents of a marine land-based fish farm. The isotopic signal in different subsamples of the macroalgae thalli (tissue that has grown during the same period) varied depending on the age of the tissue. Moreover, the isotopic signal decreased significantly with the age of the frond to within a certain range. The δ¹⁵N of F. vesiculosus is temporally unstable; therefore, measurement of the δ¹⁵N of macroalgal tissues does not allow reliable retrospective biomonitoring of environmental pollution. Further knowledge about the growth and other biological aspects of this species is required.     

Land-based nutrient enrichment of the Buccoo Reef Complex and fringing coral reefs of Tobago, West Indies

Tobago’s fringing coral reefs (FR) and Buccoo Reef Complex (BRC) can be affected locally by wastewater and stormwater, and regionally by the Orinoco River. In 2001, seasonal effects of these inputs on water-column nutrients and phytoplankton (Chl a), macroalgal C:N:P and δ¹⁵N values, and biocover at FR and BRC sites were examined. Dissolved inorganic nitrogen (DIN, particularly ammonium) increased and soluble reactive phosphorus (SRP) decreased from the dry to wet season. Wet season satellite and Chl a data showed that Orinoco runoff reaching Tobago contained chromophoric dissolved organic matter (CDOM) but little Chl a, suggesting minimal riverine nutrient transport to Tobago. C:N ratios were lower (16 vs. 21) and macroalgal δ¹⁵N values higher (6.6‰ vs. 5.5‰) in the BRC vs. FR, indicating relatively more wastewater N in the BRC. High macroalgae and low coral cover in the BRC further indicated that better wastewater treatment could improve the health of Tobago’s coral reefs.     

Trace element concentrations in barramundi (Lates calcarifer) collected along the coast of Vietnam

We determined concentrations of 23 trace elements (TEs), and stable carbon and nitrogen isotope (δ¹³C and δ¹⁵N) signatures in barramundi (Lates calcarifer) specimens collected along the coast of Vietnam in the Northern (NCZ), Central (CCZ) and Southern (SCZ) zones in the period 2007–2010. A combination of δ¹³C and δ¹⁵N signatures provided insight into ontogenetic shifts in barramundi foraging choices. There were clear zone-dependent differences in Mn, As, Sr and Tl concentrations; levels of Tl were highest in the NCZ, As in the CCZ, and Mn and Sr in the SCZ. Lowest concentrations of Rb occurred in the NCZ, Bi was lowest in the CCZ, and Cd and Cs were lowest in the SCZ. δ¹⁵N values significantly increased with increasing Zn, Se, Sn and Cs. Concentrations of TEs in barramundi from Vietnam were below worldwide guidelines for human consumption.     

Evidence for a secular variation in the13C/12C ratio of carbon implanted in lunar soils

A plot of δ¹³C against δ¹⁵N for all lunar soils and breccias for which both values are available indicates that the 30% change in δ¹⁵N previously observed is accompanied by a change in δ¹³C about one-tenth as large. The correlation remains when the data are broken down into sub-sets according to soil maturity. The correlation therefore is not due to maturation effects or non-selective sample contamination and must represent concurrent changes in the isotope ratios of both elements at their source. A rough calculation of the relative production rates of¹³C and¹⁵N indicates that spallation reactions in the sun could lead to the observed ratio of the δ¹³C to δ¹⁵N variations.     

Analyses of nitrogen and argon in single lunar grains: towards a quantification of the asteroidal contribution to planetary surfaces

We performed nitrogen and argon isotopic analyses in single 200-μm-sized ilmenite grains of lunar regolith samples 71501, 79035 and 79135. Cosmogenic and trapped components were discriminated using stepwise heating with a power-controlled CO₂ laser. Cosmogenic ¹⁵N and ³⁸Ar correlate among different ilmenite grains, yielding a mean ¹⁵N_c/³⁸Ar_c production ratio of 14.4±1.0 atoms/atom. This yields a ¹⁵N production rate in bulk lunar samples of 3.8-5.6 pg (g rock)⁻¹ Ma⁻¹, which agrees well with previous estimates. The trapped δ¹⁵N values show large variations (up to 300‰) among different grains of a given soil, reflecting complex histories of mixing between different end-members. The ³⁶Ar/¹⁴N ratio, which is expected to increase with increasing contribution of solar ions, varies from 0.007 to 0.44 times the solar abundance ratio. The trapped δ¹⁵N values correlate roughly with the ³⁶Ar/¹⁴N ratios from a non-solar end-member characterized by a ³⁶Ar/¹⁴N ratio close to 0 and variable but generally positive δ¹⁵N values, to lower δ¹⁵N values accompanied by increasing ³⁶Ar/¹⁴N ratios, supporting the claim of Hashizume et al. (2000) that solar nitrogen is largely depleted in ¹⁵N relative to meteoritic or terrestrial nitrogen. Nevertheless, the ³⁶Ar/¹⁴N ratio of the ¹⁵N-depleted (solar) end-member is lower than the solar abundance ratio by a factor of 2.5-5. We explain this by a reprocessing of implanted solar wind atoms, during which part of the chemically inert rare gases were lost. We estimate that the flux of non-solar N necessary to account for the observed δ¹⁵N values is comparable to the flux of micrometeorites and interplanetary dust particles estimated for the Earth. Hence we propose that the variations in δ¹⁵N values observed in lunar regolith can be simply explained by mixing between solar wind contributions and micrometeoritic ones infalling on the Moon. Temporal variations of δ¹⁵N values among samples of different antiquities could be due to changes in the micrometeoritic flux through time, in which case such flux has increased by up to an order of magnitude during the last 0.5 Ga.     

Anthropogenic land-use signals propagate through stream food webs in a California,USA, watershed

Human development of watersheds can change aquatic ecosystems via multiple pathways. For instance, human rural development may add nutrients to ecosystems. We used naturally occurring stable isotopes in stream food webs to investigate how land use affects stream ecosystems across a gradient of land development in the San Lorenzo watershed, California. Road density was used as a proxy for land development. We found that streams in watersheds with higher road densities had elevated concentrations of phosphate and nitrate. Furthermore, algal δ¹⁵N values increased as a function of nitrate concentration, but saturated at approximately 6‰. This saturating pattern was consistent with a two-source mixing model with anthropogenic and watershed sources, fit using Bayesian model fitting. In sites that had >2.6 km roads km⁻², anthropogenic sources of N were estimated to represent >90% of the N pool. This anthropogenic N signal was propagated to stream consumers: rainbow trout (Oncorhynchus mykiss), signal crayfish (Pacifasticus leniusculus), and benthic invertebrate δ¹⁵N were positively correlated with algal δ¹⁵N. Even relatively low density rural human land use may have substantial impacts on nutrient cycling of stream ecosystems.     

Carbon,nitrogen, and water stable isotopes in plant tissue and soils across a moisture gradient in Puerto Rico

Stable isotopes in the water molecule (²H or D and ¹⁸O), carbon, and nitrogen are useful tracers and integrators of processes in plant ecohydrological systems across scales. Over the last few years, there has been growing interest in regional to continental scale synthesis of stable isotope data with a view to elucidating biogeochemical and ecohydrological patterns. Published datasets from the humid tropics, however, are limited. To be able to contribute to bridging the “data gap” in the humid tropics, here, we publish a relatively novel and unique suite of δ¹³C, δ¹⁵N, δ²H, and δ¹⁸O isotope data from three sites across a moisture gradient and contrasting land use in Puerto Rico. Plant tissue (xylem and leaf) samples from two species of mahogany (Swietenia macrophylla and Swietenia mahagoni) and soil samples down to 60 cm in the soil profile were collected in relatively “wet” (July 2012) and “dry” (February 2013) periods at two sites in northeastern (Luquillo) and southwestern (Susua) Puerto Rico. The same sampling suite is also being made available from a highly urbanized site in the capital San Juan. Leaf samples taken in July 2012 and February 2013 were analyzed for δ¹³C and δ¹⁵N; all xylem and bulk soil samples were analyzed for δ²H and δ¹⁸O. Soil samples taken in July 2012 were analyzed for δ¹³C and δ¹⁵N. Leaf δ¹⁵N and δ¹³C dataset showed patterns that are possibly associated with site differences. While spatial patterns were also apparent in soil δ¹⁵N and δ¹³C dataset, the positively linear δ¹⁵N –δ¹³C relationship tends to weaken with site moisture. Soil depth and site moisture patterns were also observed in the δ²H and δ¹⁸O datasets of bulk soil and xylem samples. The purpose of these datasets is to provide baseline information on soil–plant water (δ²H and δ¹⁸O, N = 319), δ¹³C (N = 272), and δ¹⁵N (N = 269) that may be useful in a wide range of research questions from ecohydrological relations to biogeochemical patterns in soils and vegetation.     

Collocation of hydrological and biological attenuation of nitrate in an urban stream

The hydrologic and biogeochemical processes that control nutrient export in urban streams are not well understood. Attenuation can occur by tributary dilution, groundwater discharge, and biological processing both in the water column and the hyporheic zone. A wastewater treatment plant on Pennypack Creek, an urban stream near Philadelphia, PA, provided high nitrate concentrations for analysis of downstream attenuation processes. Longitudinal sampling for an 8‐km reach revealed decreases in nitrate concentration of 2 mg l^?1 at high flow and 4.5 mg l^?1 during low flow. During high flow, δ¹⁵N‐NO₃ increased from 9.5 to 10.5‰ and during low flow increased from 10.1 to 11.1‰. Two reaches were sampled at fine spatial intervals (approximately 200 m) to better identify attenuation processes. Mixing analysis indicated that groundwater discharge and biological processing both control nitrate concentration and isotope signatures. However, fine‐scaled sampling did not reveal spatially discrete zones; instead, these processes were occurring simultaneously. While both processes attenuate nitrate, they have opposite isotope signatures, which may have muted changes in δ¹⁵N‐NO₃. At high flow, a decrease in Cl/NO₃ ratios helped distinguish groundwater discharge occurring along both finely sampled reaches. At low flow, biological processing seemed to be occurring more extensively, but the δ¹⁵N‐NO₃ signature was not consistent with either a single process or a sequential combination of groundwater dilution and biological nitrate attenuation. The collocation of processes makes it more difficult to assess biological processing hot spots and predict how urbanization and subsequent stream restoration influence nitrate attenuation. Copyright © 2016 John Wiley & Sons, Ltd.     

Nitrogen isotope ratios of nitrate as a clue to the origin of nitrogen on the Pacific coast of Japan

To clarify the sources and transformation of NO₃⁻ on the Pacific coast of Japan, observations over the continental shelf were conducted during the summer in 2005 and 2006 when the Kuroshio flowed close to and away from the coastal area, respectively. Below the halocline, there are two prominent salinity peaks that originated in two different waters. In the subsurface layer, the salinity maximum (S_max) was indicative of the Kuroshio Water (KW), while the salinity minimum (S_min) in the middle layer at ∼400 m depth was indicative of the North Pacific Intermediate Water (NPIW). δ¹⁵N_NO3 ranged from 4.1‰ to 5.1‰ with a mean of 4.8±0.4‰ in the deeper water around S_min. Below 50 m depth over the shelf break, δ¹⁵N_NO3 values (3.1±0.8‰ in 2005 and 4.6±0.3‰ in 2006) clearly increased as contribution of NPIW increased in 2006. On the contrary, subsurface δ¹⁵N of NO₃⁻ values (−1.1±0.1‰) remained unchanged in both years, although the contribution of the KW to the subsurface water changed significantly. This suggests that the source of NO₃⁻ has little effect on the δ¹⁵N of NO₃⁻ in this layer. The negative δ¹⁵N values also coincided with the base of the chlorophyll maximum layer suggesting that these isotopic signals must be evidence of active nitrification in the upper layer.     

Changes in carbon and nitrogen cycling in a floodplain lake over recent decades linked to littoral expansion,declining riverine influx,and eutrophication

This study aimed to understand changes in the biogeochemical processing of organic matter (OM) in response to multiple stressors (e.g., littoral area expansion, wastewater input, and hydrological regulation) in East Dongting Lake (Central China) over the past 60 years, using analyses of total organic carbon (TOC), total nitrogen (TN), C/N ratios, δ¹³C, δ¹⁵N, and diatoms from 2 sediment cores collected from the littoral and central parts of the lake. OM mainly originated from phytoplankton and C₃ plant‐derived soil OM based on the ranges of C/N ratios (from 7 to 11) and δ¹³C (between ?27‰ and ?23‰). Littoral area expansion due to siltation caused an increasing influx of terrestrial soil OM in the 1980s and the 1990s, subsequently lowering δ¹³C values and rising C/N ratios in both sediment cores. Meanwhile, higher δ¹⁵N was linked to a high influx of isotopically heavy nitrate from urban and agricultural wastewaters. After 2000, slight decreases in TOC and TN in the littoral area were attributable to reducing inputs of external OM, likely linked to declining sediment influx from the upper reaches resulting from the Three Gorges Dam impoundment. Contrasting increases in TOC, TN, and C/N ratios in the central part indicated a high influx of terrestrial soil OM due to the declining distance from the shoreline with littoral area expansion. Declining δ¹⁵N values after 2000 indicated an increase in N₂‐fixing cyanobacteria with eutrophication. Changes in diatom assemblages in both the littoral and central zones reflected nutrient enrichment and hydrological alterations. These results indicate that littoral expansion, declining riverine influx, and anthropogenic nutrient inputs are potential driving forces for the biogeochemical processing of OM in floodplain lakes. This study provides sedimentary biogeochemical clues for tracking past limnological conditions of floodplain lakes that are subjected to increasing disturbances from hydrological regulation and eutrophication.