Trace elements (Cu,Zn, and Hg) and δ<Superscript>13</Superscript>C/δ<Superscript>15</Superscript>N in seabird subfossils from three islands of the South China Sea and its implications

Seabird subfossils were collected on three islands of the Xisha Archipelago, South China Sea. Via elemental analysis, we identified that bird guano was a significant source for heavy metals Cu, Zn, and Hg. Cu and Zn levels in these guano samples are comparable to their levels in wildbird feces, but guano Hg was lower than previously reported. Trophic positions significantly impacted transfer efficiency of heavy metals by seabirds. Despite of a common source, trace elements, as well as stable isotopes (i.e., guano δ¹³C and collagen δ¹⁵N), showed island-specific characteristics. Bird subfossils on larger island had relatively greater metal concentrations and revealed higher trophic positions. Partition of element and isotope levels among the islands suggested that transfer efficacy of seabirds on different islands was different, and bird species were probably unevenly distributed among the islets. Island area is possibly a driving factor for distributions of seabird species.     

Trophic dynamics of U, Ni, Hg and other contaminants of potential concern on the Department of Energy’s Savannah River Site

The Department of Energy’s Savannah River Site is a former nuclear weapon material production and current research facility located in South Carolina, USA. Wastewater discharges from a fuel and nuclear reactor target manufacturing facility released depleted and natural U, as well as other metals into the Tims Branch-Steed Pond water system. We investigated the current dynamics of this system for the purposes of environmental monitoring and assessment by examining metal concentrations, bioavailability, and trophic transfer of contaminants in seven ponds. Biofilm, detritus, and Anuran and Anisopteran larvae were collected and analyzed for stable isotopes (δ ¹⁵N, δ ¹³C) and contaminants of potential concern (COPC) with a focus on Ni, U, and Hg, to examine metal mobility. Highest levels of Ni and U were found in biofilms U (147 and 332 mg kg^?1 DW, respectively), while highest Hg levels were found in tadpoles (1.1 mg kg^?1 DW). We found intraspecific biomagnification of COPCs as expressed through stable isotope analysis. Biofilms were the best indicators for contamination and Anuran larvae with the digestive tract removed were the best indicators of the specific bioavailability of the focal metals. Monitoring data showed that baseline δ ¹⁵N values differed between ponds, but within a pond, values were stable throughout tadpole Gosner stage, strengthening the case to use this species for monitoring purposes. It is likely that there still is risk to ecosystem integrity as COPC metals are being assimilated into lower trophic organisms and even low levels of this mixture has shown to produce deleterious effects to some wildlife species.     

Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations

Gas chromatography-isotope ratio mass spectrometry (GC-IRMS) has made it possible to analyze natural stable isotope ratios (e.g., (13)C/(12)C, (15)N/(14)N, (2)H/(1)H) of individual organic contaminants in environmental samples. They may be used as fingerprints to infer contamination sources, and may demonstrate, and even quantify, the occurrence of natural contaminant transformation by the enrichment of heavy isotopes that arises from degradation-induced isotope fractionation. This review highlights an additional powerful feature of stable isotope fractionation: the study of environmental transformation mechanisms. Isotope effects reflect the energy difference of isotopologues (i.e., molecules carrying a light versus a heavy isotope in a particular molecular position) when moving from reactant to transition state. Measuring isotope fractionation, therefore, essentially allows a glimpse at transition states! It is shown how such position-specific isotope effects are "diluted out" in the compound average measured by GC-IRMS, and how a careful evaluation in mechanistic scenarios and by dual isotope plots can recover the underlying mechanistic information. The mathematical framework for multistep isotope fractionation in environmental transformations is reviewed. Case studies demonstrate how isotope fractionation changes in the presence of mass transfer, enzymatic commitment to catalysis, multiple chemical reaction steps or limited bioavailability, and how this gives information about the individual process steps. Finally, it is discussed how isotope ratios of individual products evolve in sequential or parallel transformations, and what mechanistic insight they contain. A concluding session gives an outlook on current developments, future research directions and the potential for bridging the gap between laboratory and real world systems.     

Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios

This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the ²⁰³Tl/²⁰⁵Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios (²⁰⁷Pb/²⁰⁶Pb) found were 0.85073?±?0.0004~0.85373?±?0.0003 for the main stream, while they were 0.83736?±?0.0010 for the tributary and 0.84393?±?0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60 %. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.     

Hydropower production and river rehabilitation: A case study on an alpine river

Despite the numerous benefits of hydropower production, this renewable energy source can have serious negative consequences on the environment. For example, dams act as barriers for the longitudinal migration of organisms and transport of particulate matter. Accelerated siltation processes in the receiving river reduce the vertical connectivity between river and groundwater. Hydropeaks, caused by short-term changes in hydropower operation, result in a negative impact on both habitat and organisms, especially during winter months when natural discharge is low and almost constant. In this study, we report the current deficits present in the River Rhone from two different scientific perspectives – fish ecology and hydrology. Potential rehabilitation solutions in synergy with flood protection measures are discussed. We focus on the effects of hydropeaking in relation to longitudinal and vertical dimensions and discuss local river widening as a potential rehabilitation tool. The fish fauna in the Rhone is characterized by a highly unnatural structure (low diversity, impaired age distribution). A high correlation between fish biomass and monotonous morphology (poor cover availability) was established. Tracer hydrology provided further details about the reduced permeability of the riverbank, revealing a high degree of siltation with K values of about 4.7 × 10^?6 m s^?1. Improving the hydrologic situation is therefore essential for the successful rehabilitation of the Rhone River. To this end, hydropeaks in the river reaches must be attenuated. This can be realized by a combination of different hard technical and soft operational measures such as retention reservoirs or slower up and down ramping of turbines.     

Groundwater quality assessment in semi-arid regions using integrated approaches: the case of Grombalia aquifer (NE Tunisia)

As many arid and semi-arid regions in the Mediterranean Basin, the Grombalia coastal aquifer (NE Tunisia) is affected by severe groundwater exploitation and contamination. Therefore, quality assessments are becoming increasingly important as the long-term protection of water resources is at stake. Multidisciplinary investigations, like the one presented in this paper, are particularly effective in identifying the different origins of mineralization within an aquifer and investigating the impact of anthropogenic activities on groundwater quality. An integrated assessment, focused on the combined use of geostatistical, geochemical and isotopic (δ¹⁸O, δ²H and ³H) tools, was performed in the Grombalia aquifer between February and March 2014. The overall goal was to study the main processes controlling aquifer salinization, with special focus to nitrate contamination. Results indicate a persisting deterioration of water quality over the whole basin except the south-eastern zone juxtaposing the recharge area of the aquifer. Nitrate contents exceed the drinking water standard (50 mg/l) in 70% of groundwater samples, mainly due to the excessive use of fertilizers and urban activities. Stable isotope measurements showed the contribution of modern rainwater to aquifer recharge and proved the presence of evaporation contributing to the salinity increase. Tritium values of groundwater samples suggested two hypotheses: the existence of mixture between old and recent water or/and the existence of two recharge periods of the aquifer, pre- and post-nuclear weapons test. Principal component analysis confirmed the geochemical interpretation, highlighting that water-rock interaction evaporation effect and intensive anthropogenic activities constitute the main processes controlling the regional groundwater mineralization.     

南极大气气溶胶中铅同位素比值的研究

通过对电感耦合等离子体质谱(ICP-MS)的工作条件和参数进行优化,建立了ICP-MS测定铅同位素比值的精确方法,测量了2007—2009年南极中山站采集到的气溶胶样品中208Pb/206Pb、207Pb/206Pb和206Pb/207Pb的比值。结果表明,南极大气气溶胶中铅同位素比值在逐年缓慢地发生线性变化,线性相关系数为0.996 2;气溶胶铅同位素示踪揭示南极附近国家(除南非)释放的铅可能成为南极大气中铅的重要来源。     

Calibration and Validation of Far Field Dilution Models for Outfall at Worli, Mumbai

The city of Mumbai, India with a population of 15 million discharges about 2225 MLD of domestic wastewater after partial treatment to adjoining marine water body. Under the Mumbai Sewage Disposal Project Scheme, sewage is being disposed to the west coast at Worli and Bandra through 3.4 kms long submarine outfalls. A field study was conducted at recently commissioned outfall diffuser location at Worli, at the onset of neap flood tide to study the dispersion patterns and measure the far field dilutions using radio and dye tracers. Estimated dilutions using different tracers were compared with outputs from an empirical model (Brooks) and a 2D numerical model (DIVAST). Validation using parameters such as BOD and FC, indicated a good match for BOD in near field compared to FC. The radiotracer ⁸²Br and Rhodamine WT generally gave good correlation with Brooks' and DIVAST models for nearfield, however at further distances predictions were not accurate.     

Application of SMR to Modeling Watersheds in the Catskill Mountains

Very few hydrological models commonly used in watershed management are appropriate for simulating the saturation excess runoff. The Soil Moisture Routing model (SMR) was developed specifically to predict saturation excess runoff from variable source areas, especially for areas where shallow interflow controls saturation. A recent version of SMR was applied to two rural catchments in the Catskill Mountains to evaluate its ability to simulate the hydrology of these systems. Only readily available meteorological, topographical, and landuse information from published literature and governmental agencies was used. Measured and predicted streamflows showed relatively good agreement; the average Nash–Sutcliffe efficiency for the two watersheds were R ²=72% and R ²=63%. Distributed soil moisture contents and the locations of hydrologically sensitive areas were also predicted well.     

Enrichment of <Superscript>15</Superscript>N/<Superscript>14</Superscript>N in wastewater-derived effluent varies with operational performance of treatment systems: implications for isotope monitoring in receiving environments

Stable nitrogen isotope ratios are routinely used to trace the dispersion and assimilation of wastewater-derived N in receiving environments, but few isotope studies have investigated wastewater treatment plants and ponds themselves. An improved understanding of N isotope compositions in effluent will help assess treatment plant processes and performance and will help trace sources of excess nutrients in receiving environments. Here, we assess N budgets and treatment processes in seven wastewater treatment plants and wastewater stabilisation ponds in northern Australia based on concentrations and isotope ratios of N in effluent. We show that δ¹⁵N values in effluent are linked to treatment type, effectiveness of conversion of ammonia and levels of gaseous N emissions. These relationships suggest that N isotope monitoring of wastewater treatment plants and ponds can provide an integrated assessment of treatment performance and gaseous N emissions on a pond- or plant-wide scale that is not readily available through other methods. Our findings further imply that monitoring N isotope ratios in receiving environments cannot be assumed to be universally effective as their sensitivity to uptake of wastewater-derived N will vary with the characteristics of individual treatment systems. Paradoxically, N isotope monitoring is less effective where treatment systems are functioning poorly and where monitoring needs are the greatest.