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Pyrite is a typical sulfide mineral which contains various potentially toxic metal(loid)s (PTMs). The pyrite smelting and subsequent industrial utilization activities usually release numerous amounts of PTMs into nearby ecosystem, which may be enriched in the nearby farmland soils and crops, leading to hidden but irreversible harm to human health via the food chain. Herein, the distribution pattern, source apportionment, and potential health risks of Pb, Zn, Cu, Cd and multiple seldom monitored PTMs (Ag, Bi, Sb, Sr, Th, U, W, and V) in the paddy soils and different organs of the rice plants from ten various sites in a typical industrial zone were investigated, where pyrite ores were used for the production of sulfuric acid and subsequent cement over several decades. The results showed that the contents of Cd, Pb and Zn in studied paddy soils generally exceeded the maximum permissible level (MPL) in China, and the contents of Sb and V were approaching the MPL. Moreover, the rice is easier to bioaccumulate Cd, Cu, and Zn than the other studied elements. The hazard quotient (HQ) calculations indicate that the rice containing such multiple elements may cause a high potential non-carcinogenic and carcinogenic health risk for residents, particularly for the senior group. The Pb isotope tracing method combined with PCA (principal component analysis) further uncovered that the pyrite industrial utilization contributed 18.58-55.41 % to the highly enriched PTMs in paddy soils. All these findings indicate that the paddy soil system has been contaminated by the pyrite industrial activities and certain distances or areas should be rigidly forbidden from rice cultivation in the proximity of the pyrite smelting and related industrial sites.

With the gradual increase of the coal mining depth, the mixing of multiple water sources intensifies and the activity of radium and radon in groundwater increases. Identifying the source of mine water inrush by using radium and radon isotopes is a new choice. In this paper, the mathematical statistics method, radioactive isotope decay theory, the mass conservation principle, and the numerical simulation method are used to analyze the influence of total dissolved solids (TDS), pH, and the hydrochemical ion content in groundwater on the isotope activity of radium, radon, uranium, thorium, and lead. The activity of thorium and lead is lower than the detection limit of the instrument, and the influence of coal mining activities on it is small. The simulation of the radium-radon mass balance in groundwater shows that the greater the adsorption coefficient (k) of solid particles in groundwater is, the more obvious the adsorption effect and the greater the influence on the radium-radon activity balance are. The radium-radon dating method is used to calculate the groundwater age. Results show that the groundwater age in the closed pit coal mining area is generally older than that in the mining coal mining area. Combined with the

Cadmium production has risen 1000-fold in the past 100 years, from under 20 to over 20,000 tons per year, causing anthropogenically-mobilized Cd to overwhelm natural sources in global cycling. Cadmium has no known biological function in humans, yet has biochemical behaviors similar to zinc and manganese, making exposure detrimental to human health. Identifying and quantifying the sources of Cd for human sub-populations is key to reducing exposures. Cadmium stable isotopes may provide a method for tracing Cd sources throughout the environment and the human body, but at present the limited database for high precision Cd isotopic compositions is inadequate to support such an analysis. Here, we provide new Cd isotope data on dietary sources, cigarette smoking components, and environmentally relevant standard reference materials. Results indicated that minor but significant variations are observed in food products (e.g., peanuts, sunflower seeds, spinach, kale, lettuce, cocoa powder; ~0.9‰ at 4 amu) that may be useful for tracing contamination in agricultural soils. In contrast, Cd isotope fractionation during smoking is larger (~6‰ at 4 amu) and has implications for tracing cadmium sources from tobacco combustion in the environment and throughout the human body. The primary inhaled component of cigarette smoke contains highest delta values (δ116/112Cd or δ114/110Cd ~5.2‰), while the second-hand smoke and cigarette ash have the lowest delta values (δ116/112Cd or δ114/110Cd ~−0.9‰). Used cigarette butts have δ114/110Cd ~2.4‰, in between the values measured in ash/s hand smoke and the inhaled smoke components. The high delta values of the inhaled smoke indicate that Cd isotopes may be used to determine the extent of Cd exposure due to smoking in human biological samples. This study provides new data for previously uncharacterized isotopic reservoirs that can be included in future studies of Cd source-exposure tracing.

Our current understanding of controls on δ

Isotopic analysis has seen significant use in archaeological sciences to date objects, determine their origin, and depict ancient human dietary habits. However, the potential of this technique for provenance studies of ancient silks remains underdeveloped. In this study, we applied Sr isotopic ratios to the provenance tracing of silkworm cocoons. We investigated the

The concentration and speciation of endogenous cadmium (Cd) in soil systems derived from parent materials is continuously altered by rock-soil-plant interactions. Previous studies on the distribution of Cd primarily focused on surface soil at regional scale. However, it lacks a novel approach to provide a new perspective on dynamics and redistribution of Cd in soil profile. Therefore, this study tries to establish the linkage between isotope fractionation and environmental processes of Cd in soil profiles with geogenic Cd enrichment based on Cd isotopes. High Cd concentrations were observed in the profile from forest at accumulation zone and the one from farmland at ridge in a rural area, southwest China. Soil erosion and deposition substantially influence the vertical distribution of total Cd in soil from the accumulation zone. Accordingly, distinct Cd isotope compositions were observed in different layers (δ

Permafrost degradation and the development of thermokarst lakes are important factors driving the variability of regional hydrologic processes. Hydrogeochemical and isotopic analyses are important methods for investigating the hydrologic processes of thermokarst lakes. This study focused on comparing the chemical and hydrogeochemical characteristics between lake water and groundwater during the melting of the active layer in a typical thermokarst lake region on the Qinghai-Tibet Plateau (QTP). Ninety-five samples were collected during different periods of active layer melting and analyzed using statistical, isotope, hydrogeochemical, and modeling methods. Statistical results showed that the average concentrations of almost all ions were lower in lake water than in groundwater, with wider spatial variability in groundwater. The lake water is of the ClNa and HCO

High concentrations of metal(loid)s in phosphate rocks and wastewater associated with phosphate mining and fertilizer production operations pose potential contamination risks to water resources. Here, we propose using Sr isotopes as a tracer to determine possible water quality impacts induced from phosphate mining and fertilizers production. We utilized a regional case study in the northeastern Negev in Israel, where salinization of groundwater and a spring have been attributed to historic leaking and contamination from an upstream phosphate mining wastewater. This study presents a comprehensive dataset of major and trace elements, combined with Sr isotope analyses of the Rotem phosphate rocks, local aquifer carbonate rocks, wastewater from phosphate operation in Mishor Rotem Industries, saline groundwater suspected to be impacted by Rotem mining activities, and two types of background groundwater from the local Judea Group aquifer. The results of this study indicate that trace elements that are enriched in phosphate wastewater were ubiquitously present in the regional and non-contaminated groundwater at the same levels as detected in the impacted waters, and thus cannot be explicitly linked to the phosphate wastewater. The

Phthalates, bisphenols (BPs), and terephthalic acid (TPA) are widely used plasticizers and monomers in plastic manufacturing. Most of them are known to have an adverse effect on the human body, functioning as endocrine disruptors and suspected carcinogens. Access to near real-time data on population exposure to plasticizers is essential for identifying vulnerable communities and better protecting and managing public health locally. The objective of the present study was to evaluate population-level exposure to phthalates, BPs, and TPA by measuring urinary metabolites in community wastewater. Composited community wastewater (24-h samples) from five sewer sub-catchments of a southwestern city within the United States were analyzed for urinary biomarkers of phthalates, BPs, and TPA using solid-phase extraction-liquid chromatography-tandem mass spectrometry in conjunction with the isotope dilution method for absolute quantification. Ten of 16 analytes were detected at least once in community wastewater above the method detection limit (MDL), with MDLs ranging from 37 to 203 ng/L. The population normalized mass load of TPA was the highest, followed by the human metabolite of di-(2-ethylhexyl) phthalate (DEHP). Bisphenol S and monoethyl phthalate were detected with the highest frequency. Study findings suggest that analyzing municipal wastewater for chemical indicators of human exposure to plastic constituents is feasible, practicable, and informative, as long as appropriate steps are taken to determine, quantify and account for background levels of plastic analytes in the laboratory environment.

Tris(2-chloroethyl) phosphate (TCEP), as a typical chlorinated flame retardant, is attracting more attention as a carcinogen. Although persulfate-based oxidation exhibits good performance in removing refractory organic pollutants, the kinetics of persulfate-based remediation are affected by inorganic anions, which causes inaccurate remediation efficiency. This study combines steady-state radical concentration modelling with isotope fractionation to investigate the effects of inorganic anions on TCEP degradation by UV/persulfate (UV/PS). In the absence of anions during UV/PS system, the observed degradation rate was (9.7 ± 0.1) × 10

The intensive use of copper (Cu) compounds as an alternative biocide in antifouling paints (APs) has resulted in wide Cu contamination into the marine environment, especially near marina harbor activities. In this work, the applicability of Cu isotopes to discriminate Cu origins related to the use of Cu-based APs in marine environments was tested. To this, Cu isotopes in APs, shipyard sludges, and sediment cores sampled in the Cu-contaminated Mediterranean marina of Port Camargue were determined. APs represent an important dominant anthropogenic source for metals in this site, making it ideal to test Cu isotopes as tracers. The overall isotope composition of four sediment cores and a surface sample varied between -0.13 and 0.44 ‰ (δ

The inter-mountainous region of central Honduras has been experiencing abrupt urban drinking water shortages during the last decade. Land use fragmentation and rainfall deficits have rapidly reduced surface water quality and quantity in this region. Here we present a 3-yr (2018-2020) tracer study within the headwaters of the Choluteca River basin (2949 km

As a component of many minerals and an essential trace element in most aerobic organisms, the transition metal element Cu is important for studying reduction-oxidation (redox) interactions and metal cycling in the total environment (lithosphere, atmosphere, biosphere, hydrosphere, and anthroposphere). The "fractionation" or relative partitioning of the naturally occurring "heavy" (

Dissolved oxygen (DO) dynamics of a temperate drinking water reservoir in the Harz Mountains (Germany) were investigated over a time period of 18 months. Via depth profiles in a fortnightly sampling resolution we were able to trace DO and temperature dynamics including the formation and breakdown of a Metalimnetic Oxygen Minimum (MOM) by means of DO concentration, saturation patterns and stable isotope ratios of dissolved oxygen (expressed as δ

Organic matter (OM) tracing is critical for understanding the processes of soil redistribution and global carbon cycling. It effectively supports ecological management and global climate change prediction. Stable isotopes are generally more source-specific compared with other tracers and identify OM sources with a higher level of accuracy. Nevertheless, stable isotopes may be enriched or depleted by physical and biochemical processes such as selective migration of particles and OM mineralization in transport and sedimentary environments, making it difficult to establish links between the source and sink regions. Literature on OM source identification tends to assume a direct link between stable isotope sources and sinks, ignoring the non-conservatism of stable isotopes. There is further literature on understanding and modeling the processes that link the sources to sinks in terms of the non-conservatism of stable isotopes. The disagreement in response to the non-conservatism lies in the lack of comprehensive understanding of stable isotope fingerprinting systems and non-conservatism. The development of stable isotope fingerprinting technology is full of challenges. This review outlines the applicability of stable isotope tracers, identification mechanisms, and associated quantitative models, intending to improve the stable isotope fingerprinting system. We highlight the non-conservatism of stable isotopes in space and time caused by physical and biochemical processes. Additionally, a decision tree is established to determine the quantitative tools, evaluation indicators, and procedures related to non-conservatism. This decision tree clarifies the process from non-conservatism detection to threshold determination of statistical quantification, which can guide the end-users to better apply stable isotope to trace OM sources.

Climate change and associated droughts threaten the ecology and resilience of natural saline lakes globally. There is a distinct lack of research regarding their ecological response to climatic events in the Global South. This region is predicted to experience climatic events such as El Niño-Southern Oscillation (ENSO) more often and with greater severity with the potential to alter the structure and functioning of aquatic ecosystems significantly. From 2015 to 2016 South Africa experienced one of the most severe country-wide droughts as a result of a strong ENSO event. Our study aimed to investigate the effect of this supra-seasonal drought on the trophic structure of fish communities in a naturally saline shallow lake of a Ramsar wetland using stable isotope techniques. Fishes and potential basal sources were collected from the lake, during predrought conditions in 2010 and after severe drought (recovery phase; 2017). The δ

Northern Chile, NW Argentina, and SW Bolivia, ("the lithium triangle"), represent a world class reservoir of lithium, but this extraordinary enrichment is still controversial, and different processes have been invoked over the years, including, geothermal waters associated with active volcanism, leaching of soluble salts from volcanic rocks and leaching of lithium-rich clays. The Salar de Atacama (SDA) represents one of the richest reservoirs of Li in northern Chile and has been extensively studied during the past years. Most of the studies have been focused in the southern and southeastern portions, where the highest lithium concentrations have been reported. However, a comprehensive model of water recharge at SDA is still imprecise. We used a combination of isotopic methods, including δ

This paper reports Pb isotopes in different fractions following the three step BCR and 1 M HCl extractions on river sediments from lower reaches of the Xiangjiang river in China, and highlights the importance of Pb isotopes in heavy metal contamination assessment. Lead concentrations and Pb isotopes in bulk sediments and sediment fractions (leachates and residues) from the river were analysed using ICP-MS techniques. Results showed that sediments were highly enriched with Pb with enrichment factors5.5, while Pb in sediments was dominated by reducible and residual Pb fractions, residing mainly in Fe-oxide and silicate minerals. Pb isotopes in sediments was characterized by radiogenic Pb produced from the decay of uranium and thorium with

Lakes are important paleoenvironmental archives retaining abundant information due to their typical high sedimentation rates and susceptibility to environmental changes. Here, we scrutinize the organic matter (OM) composition, origin and preservation state in surface sediments from five lakes in a remote, warming-sensitive, and poorly explored region partially covered by the retreating Collins Glacier in King George Island (Antarctica), the Fildes Peninsula. Lipid biomarkers of terrestrial origin (i.e. high-molecular weight n-alkanes, n-alkanoic acids, and n-alkanols; β-sitosterol, campesterol, and stigmasterol) were detected in the five Fildes Lakes, with the smallest basin (i.e., Meltwater) showing a particularly strong moss imprint. Aquatic source indicators such as low C/N and terrestrial over aquatic ratios (TAR), or less negative δ13C values were preferentially found in the mid-sized lakes (i.e., Drake and Ionospheric). Sedimentary carbon in the larger lakes (i.e., Uruguay and Kitezh) displayed a largely biogenic origin (i.e., values of carbon preference index, CPI, ≫1), whereas the three lakes close to Collins Glacier (i.e., Drake, Meltwater, and Ionospheric) showed certain contribution from petrogenic sources (CPI ~ 1). The results suggest that the geochemical signature of the surface sediments in the five Fildes lakes is determined by factors such as the distance to the retreating Collins Glacier, the proximity to the coast, or the lake depth. This study illustrates the forensic interest of combining lipid biomarkers, compound-specific isotopic analysis, and bulk geochemistry to reconstruct paleoenvironments and study climate-sensitive regions.

Understanding the fate of fecal pollution in the landscape is required for microbial risk analysis. The aim of this study was to assess the patterns and dynamics of beta-D-glucuronidase (GLUC), which has been suggested as a surrogate for fecal pollution monitoring, in a stream draining an agricultural headwater catchment. Automated enzymatic on-site measurements of stream water and sediments were made over two years (2014-2016) to quantify the sources and pathways of GLUC in a stream. The event water fraction of streamflow was estimated by stable isotopes. Samples from field sediments on a hillslope, streambed sediment and stream water were analyzed for GLUC and with a standard E. coli assay. The results showed ten times higher GLUC and E. coli concentrations during the summer than during the winter for all compartments (field and streambed sediments and stream water). The E. coli concentrations in the streambed sediment were approximately 100 times those of the field sediments. Of the total GLUC load in the study period, 39% were transported during hydrological events (increased streamflow due to rainfall or snowmelt); of these, 44% were transported when the stream contained no recent rainwater. The results suggested that a large proportion of the GLUC and E. coli in the stream water stemmed from resuspended streambed sediments. Moreover, the results strongly indicated the existence of remnant populations of GLUC-active organisms in the catchment. usc Refereed/Peer-reviewed

Ambient air particulate matter (PM) was collected at the Wood Buffalo Environmental Association Bertha Ganter Fort McKay monitoring station in the Athabasca Oil Sand Region (AOSR) in Alberta, Canada from February 2010 to July 2011 as part of an air quality source assessment study. Daily 24-hour duration fine (PM2.5) and coarse (PM10–2.5) PM was collected using a sequential dichotomous sampler. 100 pairs of PM2.5 and PM10–2.5 were selected for lead (Pb) concentration and isotope analysis. Pb isotope and concentration results from 250 epiphytic lichen samples collected as far as 160 km from surface mining operations in 2008, 2011, and 2014 were analyzed to examine longer term spatial variations in Pb source contributions. A key finding was recognition of thorogenic 208Pb from eastern Asia in the springtime in the PM2.5 in 2010 and 2011. 206Pb/207Pb and 208Pb/207Pb isotope ratios were used in a three-component mixing model to quantify local, regional, and global Pb sources in the PM and lichen data sets. 47 ± 3% of the Pb in the PM2.5 at AMS-1 was attributed to sources from eastern Asia. Combined results from PM10–2.5 and PM2.5 indicate PM2.5 Pb contributions from eastern Asia (34%) exceed local AOSR sources of PM2.5 Pb (20%), western Canada sources of PM2.5 Pb (19%), and PM10–2.5 Pb from fugitive dust including oil sands (14%), tailings (10%), and haul roads (3%). The lichen analysis indicates regional sources contribute 46% of the Pb, local sources 32%, and global sources 22% over the 2008–2014 timeframe. Local sources dominate atmospheric Pb deposition to lichens at near field sites (0–30 km from mining operations) whereas regional Pb sources are prevalent at distal sites (30–160 km). The Pb isotope methodology successfully quantified trans-Pacific transport of Pb to the AOSR superimposed over the aerosol footprint of the world's largest concentration of bitumen mining and upgrading facilities.

Sedimentary δDn-alkane value is widely utilized as a reliable proxy for paleo-hydrological reconstruction. Applications of this proxy must be based upon a globally clear understanding of the relationship between leaf wax δDn-alkane values and precipitation δD (δDp), defined as apparent fractionation (eapp). However, there is a critical concern about whether relatively constant eapp values exist across different latitudes. In this study, we systematically analyzed the variations of available eapp with latitudes based upon two compiled-new databases of higher plants and sediments over the world. We found that the total average eapp was relatively constant, i.e., −116 ± 5‰ (n = 941), in higher plants across different latitudes without consideration of plant types (e.g., dicots, monocots, gymnosperms), and was still constant but slightly lower average eapp, i.e., −125 ± 6‰ (n = 460), in sediments across the latitudes. The slightly lower average eapp in sediments relative to higher plants probably derived from the contribution of aquatic plants with isotopically D-depleted eapp in lake sediments. Interestingly, with consideration of plant types, average eapp increased in dicots but decreased in monocots slightly from low to high latitudes. The counteraction of these competing trends generates relatively constant average eapp values in higher plants, and resultantly constant average eapp values occur in sediments at the global scale. It is important to elaborate relatively constant eapp values from higher plants and sediments across different latitudes when sedimentary δDn-alkane is utilized as a proxy for paleohydrological reconstruction.

Calcium is a critical element in the global carbon cycle due to its role in carbon sequestration via silicate weathering and carbonate formation. Here we apply calcium (δ

Biogeochemistry patterns in shallow lakes are influenced by both in-lake factors such as ecosystem state as well as watershed-level factors such as land use, but the relative importance of in-lake versus watershed factors is poorly known. This knowledge gap makes it difficult for lake mangers to prioritize efforts on watershed versus in-lake strategies for stabilizing the clear-water state. We studied 48 shallow lakes in Minnesota, USA to assess the relative influence of lake size, land use in watersheds, and ecosystem state (turbid versus clear) on water column total nitrogen (TN) and total phosphorus (TP), as well as δ

The transformation and mobility of heavy metals and synthetic pesticides in soil depend on ageing, involving their chemical and physical distributions among soil fractions over time. Heavy metals and synthetic pesticides often co-occur in soil, although their ageing is usually evaluated separately and in bulk soil. Here, contrasting vineyard and crop soils were spiked with copper (Cu; 700 mg kg

Honeybees and their products are useful biomonitors of metal distribution in urban centres. This study investigates particulate sources that foraging honeybees encounter in Metro Vancouver. Metal concentrations and lead (Pb) isotope compositions were measured in topsoil (top 2 cm, n = 14) colocated with existing research hives and in particulate matter ≤10 μm (PM

To decipher Cu migration in paddy soils, which is important for understanding Cu supply in rice cultivation, Cu concentrations and isotope compositions were measured in a paddy soil profile in Suzhou, Eastern China, in the central Yangtze Delta. The results show that the variations in δ

Studying cadmium (Cd) transport in plants will improve the current understanding of Cd tolerance mechanisms. Due to the influence of analytical techniques, the application of Cd isotopes in plants is still in its early stages. Therefore, the relationships between Cd isotope fractionation and Cd translocation in plants remain unclear. In this study, we cultured Ricinus communis in hydroponic solutions during split/cut-root experiments and limited and infinite nutrient experiments. To understand the Cd transport process, the Cd

The micronutrient cycling in tropical latitudes is an issue of great concern because tropical soils are not only suffering micronutrient deficiency, but also influencing the global cycling of trace metals. With the development of stable isotope techniques, Zn isotopic composition (δ

The chemical composition and redox conditions of the Precambrian ocean are key factors for reconstructing the temporal evolution of atmospheric oxygen through time. In particular, the isotopic composition of iron are useful proxies for reconstructing paleo-ocean environments. Yet, respective processes and related signatures are poorly constrained, hindering the reconstruction of iron redox mechanisms in the Archean ocean. This study centers on Sihailongwan Lake, a stratified water body with a euxinic lower water column considered as an Archean ocean analogue. Results show that the anaerobic oxidation layer is so different from other similar lakes in which dissolved Fe oxidation is present in redoxcline layer. And the fractionation factor between ferrous Fe and iron hydroxide observed in nature water body of Sihailongwan Lake reaches to 2.6‰, which would benefit the production of the oxidations of BIF in sediment. By the spatial distribution of Fe isotope, the benthic water in autumn and the hypolimnetic anoxic water in spring has been identified as iron sulfide zone, where iron isotopic fractionation factor during iron sulfide formation is 1.16‰, accounting for partial scavenging of dissolved Fe(II) with an associated isotopic fractionation. However, pyrite in the sediment records the iron isotopic signal from the redoxcline but not in the iron sulfide or oxide zones of the water column. Above findings indicate that neither the iron isotope fractionation during partial transfer of ferrous iron to iron sulfide nor the partial oxidation of ferrous iron are recorded as pyrite in sedimentary rock. Importantly, the signal of Fe isotopic fractionation in water was archived in the suspended particulate matter and transferred into the sediment, rather than via ferrous iron directly deposited in the sediment. This study reveals that Fe isotopes from modern natural environments are useful proxies for reconstructing iron oxidation-reduction process during Earth's early history.

There is an increasing interest in treatment of oil sands process water (OSPW) via biofiltration with petroleum coke (PC) as a substratum. In fixed bed biofilters (FBBs) with PC, the dominance of anaerobic digestion of dissolved organics results in poor removal of naphthenic acids (NAs) along with a high degree of methanogenesis. In this study, operation of FBBs was modified to improve OSPW remediation by supporting the filtering bed with aerobic naphthenic acid-degrading bacteria treating aerated OSPW (FBBbioaugmentation). The results were compared with a biofilter operated under controlled conditions (FBBcontrol). To this end, a consortium of three aerobic NAs-degrading bacterial strains was immobilized on PC as a top layer (10 cm). These bacteria were pre-screened for growth on 15 different NAs surrogates as a sole carbon source, and for presence of catabolic genes coding alkane hydroxylase (CYP153) and alkane monooxygenase (alkB) enzymes. The results illustrated that biofiltration in FBBbioaugmentation removed 32% of classical NAs in 15 days; while in the FBBcontrol, degradation was limited to 19%. The degradation of fluorophore (aromatic) compounds was also improved from 16% to 39% for single ring (OI), 22% to 29% for double ring (OII), and 15% to 23% for three rings (OIII) compounds. DNA-Stable Isotope Probing revealed that potential hydrocarbons degraders such as Pseudomonas (inoculated), Pseudoxanthomonas (indigenous) were present up to 5.0% in the 13C-labelled DNA fraction. Furthermore, a high abundance of methylotrophs was observed in the Schmutzdecke, with Methylobacillus comprising more than two-third of the total community. This study shows that bioaugmentation rapidly improved OSPW remediation. Aeration mostly contributed to methane consumption in the top layer, thus minimize its release into the environment.

In this study, honeybees were used to determine spatio-temporal variations and origin sources of Pb. Lead concentrations and isotopic composition were used in combination with selected statistical methods. The sampling was carried out at five different locations in Serbia: urban region (BG), petrochemical industry (PA), suburban region (PV), rural region (MS) and thermal power plant region (TPP) during 2014. At PA and PV locations, samples were taken during multiple years. This is the first use of Kohonen self-organizing map (SOM) in combination with honeybees as bioindicators to determine spatio-temporal variations and origin of Pb pollution. It was observed that during the years Pb concentrations were in decline. Anthropogenic sources are most dominant in BG and TPP, in PA there are mixed sources of natural and anthropogenic origin and in PV Pb is of natural origin. It can be concluded that honeybees in combination with SOM can be used to differentiate between slight changes in spatio-temporal variations of Pb, as well as for source appointment. (C) 2018 Elsevier B.V. All rights reserved.

Uranium (U) pollution in groundwater has become a serious problem worldwide. Even in low concentrations, U has both radiological and toxicological impacts on human health. In this study an integrated hydrogeological approach was applied to conceptualize an aquifer system, and determine the origin of U detected in the aquifer of the eastern Halkidiki region in northern Greece. Data from measurements of groundwater level and hydrochemical and stable isotope analyses of groundwater samples were applied to perform geochemical modeling and multivariate statistical analysis. The modeling and statistical analysis identified three hydrogeochemical groups within the studied hydro-system, and U(VI) as the dominant U species. The first group is linked to the deeper aquifer which is characterized by water-rock interactions with weathering products of granodiorite. In this group the dominant U species is uranyl phosphate and U concentration is 3.7 μg/L. The upper aquifer corresponds to the second hydrogeochemical group where U concentrations are mainly influenced by high concentrations of nitrogen species (NO3− and NO2−). Factor analysis further discriminated the upper aquifer into a saline coastal zone and an inland zone impacted by agricultural activities. The third hydrogeochemical group presents the highest concentration of U (up to 15 μg/L) in groundwater and corresponds to the internal aquifer system. The U within this system is triggered by the presence of Mn2+, while the long residence time of the groundwater contributes synergistically to the hydrogeochemical process. Manganese triggers U oxidation in parallel with Fe2+ precipitation that acts as a regulator of U concentration. Groundwater depletion of the upper aquifers promotes the up-coning of geothermal fluids from fault zones leading to increased concentrations of U in the mid-depth aquifers.

Benzo[a]pyrene (BaP) is a typical high-molecular-weight PAH with carcinogenicity. Rhizoremediation is commonly applied to remove soil BaP, but its mechanism remains unclear. The role of inducers in root exudates in BaP rhizoremediation is rarely studied. Here, to address this problem, we firstly investigated the effect of the inducer salicylic acid on BaP rhizoremediation, rhizosphere BaP degraders, and PAH degradation-related genes by combining DNA-stable-isotope-probing, high-throughput sequencing, and gene function prediction. BaP removal in the rhizosphere was significantly increased by stimulation with salicylic acid, and the rhizosphere BaP-degrading microbial community structure was significantly changed. Fourteen microbes were responsible for the BaP metabolism, and most degraders, e.g. Aeromicrobium and Myceligenerans, were firstly linked with BaP biodegradation. The enrichment of the PAH-ring hydroxylating dioxygenase (PAH-RHD) gene in the heavy fractions of all

Lakes constitute an important part of the hydrological cycle on continents. Recent developments in high-resolution laser spectroscopy made feasible triple-isotope, high-precision analyses of water samples (δ2H, δ18O and δ17O). We conducted in-depth, comprehensive assessment of the potential and usefulness of the triple-isotope mass balance approach to quantify water budget of lakes and surface water bodies. A small, groundwater-controlled lake located in the vicinity of Krakow, southern Poland, was selected for this purpose. Approximately 30% higher incoming and outgoing groundwater fluxes derived from 2H-based budget, when compared to 18O- and 17O-based budgets, were obtained when isotopic composition of ambient moisture interacting with the lake was assumed to be in isotopic equilibrium with the local precipitation. Since the ambient moisture interacting with a given lake is in fact a mixture of the vapour released by the evaporating surface water body and the free-atmosphere water vapour, we proposed the procedure to calculate the isotopic composition of this mixture. This approach led to fully consistent triple-isotope mass balance of the studied lake. The underground water fluxes derived separately for the three isotope tracers in use (2H, 18O and 17O) turned out to be identical within the quoted uncertainties, thus supporting internal consistency of the obtained results. The magnitude of the calculated fluxes was in the order of 3200 mm year−1 for the incoming groundwater flux and 3100 mm year−1 for underground losses of lake water through seepage to the local aquifer. The calculated mean turnover time of water in the studied lake is only ca. 16 months, which guarantees a good quality of lake water, a critical parameter in the light of intensive exploitation of this lake as a popular recreational destination during summer.

Heavy metal accumulation in marine sediments is associated with changes in both the natural environment and human activities. This study used heavy metals and Pb isotopes in a precisely dated (by 210Pb and 137Cs) sediment core from the Macao Sea to reconstruct the historical changes in anthropogenic activities and the environment in the western Pearl River Estuary (PRE). The distribution of heavy metals in the sediment core could be divided into four stages (pre-1950, 1950–1976, 1976–2000, and post-2000), which corresponded to the changes in anthropogenic activities and environment of the Pearl River Delta during the past 100 years. The contribution of anthropogenic metals (Pb and Zn) in the sediments increased gradually over time. However, the concentrations, enrichment factors, and fluxes of heavy metals in the sediments all displayed a downward trend since 2010, revealing a decline in metal pollutant input due to strict emission reduction policies implemented in the last decade. The Pb isotopes in the sediments showed a similar trajectory to the heavy metals, reflecting the changes in Pb sources in the sediments at different stages. Based on a binary Pb isotope mixing model, the calculated proportions of anthropogenic and natural Pb in the sediments were 0–50.9% (mean 15.9%) and 49.1–100% (mean 84.1%), respectively, suggesting that the Pb in the PRE sediments is mainly controlled by natural sources.

Multiple processes are involved in Cd transfer in rice plants, including root uptake, xylem loading, and immobilization. These processes can be mediated by membrane transporters and can alter Cd speciation by binding Cd to different organic ligands. However, it remains unclear which processes control Cd transport in rice in response to different watering conditions in soil. Herein, Cd isotope fractionation and Cd-related gene expression were employed to investigate the key regulatory mechanisms during uptake, root-to-shoot, and stem-to-leaf transport of Cd in rice grown in pot experiments with Cd-contaminated soil under flooded and non-flooded conditions, respectively. The results showed that soil flooding decreased the Cd concentration in soil porewater and, thereby, Cd uptake and transport in rice. Cd isotopes fractionated negatively from soil porewater to the whole rice (flooded: ∆114/110Cdrice-porewater = −0.15‰, non-flooded: ∆114/110Cdrice-porewater = −0.39‰), suggesting that Cd transporters preferentially absorbed light Cd isotopes. The non-flooded treatment revealed an upregulated expression of OsNRAMP1 and OsNRAMP5 genes compared to the flooded treatment, which may partially contribute to its more pronounced porewater-to-rice fractionation. Cd isotopes fractionated positively from roots to shoots under flooded conditions (∆114/110Cdshoot-root = 0.19‰). However, a reverse direction of fractionation was observed under non-flooded conditions (∆114/110Cdshoot-root = −0.67‰), which was associated with the substantial upregulation of CAL1 in roots, facilitating xylem loading of Cd-CAL1 complexes with lighter isotopes. After being transported to the shoots, the majority of Cd were detained in stems (44%–55%), which were strongly enriched in lighter isotopes than in the leaves (∆114/110Cdleaf-stem = 0.77 to 1.01‰). Besides the Cd-CAL1 transported from the roots, the expression of OsPCS1 and OsHMA3 in the stems could also favor the enrichment of Cd-PCs with lighter isotopes, leaving heavier isotopes to be transported to the leaves. The higher expression levels of OsMT1e in older leaves than in younger leaves implied that Cd immobilization via binding to metallothioneins like OsMT1e may favor the enrichment of lighter isotopes in older leaves. The non-flooded treatment showed lighter Cd isotopes in younger leaves than the flooded treatment, suggesting that more Cd-CAL1 in the stems and Cd-PCs in the older leaves might be transported to the younger leaves under non-flooded conditions. Our results demonstrate that isotopically light Cd can be preferentially transported from roots to shoots when more Cd is absorbed by rice under non-flooded conditions, and isotope fractionation signature together with gene expression quantification has the potential to provide a better understanding of the key processes regulating Cd transfer in rice.

The Arctic terrestrial environment harbors a complex mosaic of mercury (Hg) and carbon (C) reservoirs, some of which are rapidly destabilizing in response to climate warming. The sources of riverine Hg across the Mackenzie River basin (MRB) are uncertain, which leads to a poor understanding of potential future release. Measurements of dissolved and particulate mercury (DHg, PHg) and carbon (DOC, POC) concentration were performed, along with analyses of Hg stable isotope ratios (incl. ∆199Hg, δ202Hg), radiocarbon content (∆14C) and optical properties of DOC of river water. Isotopic ratios of Hg revealed a closer association to terrestrial Hg reservoirs for the particulate fraction, while the dissolved fraction was more closely associated with atmospheric deposition sources of shorter turnover time. There was a positive correlation between the ∆14C-OC and riverine Hg concentration for both particulate and dissolved fractions, indicating that waters transporting older-OC (14C-depleted) also contained higher levels of Hg. In the dissolved fraction, older DOC was also associated with higher molecular weight, aromaticity and humic content, which are likely associated with higher Hg-binding potential. Riverine PHg concentration increased with turbidity and SO4 concentration. There were large contrasts in Hg concentration and OC age and quality among the mountain and lowland sectors of the MRB, which likely reflect the spatial distribution of various terrestrial Hg and OC reservoirs, including weathering of sulfate minerals, erosion and extraction of coal deposits, thawing permafrost, forest fires, peatlands, and forests. Results revealed major differences in the sources of particulate and dissolved riverine Hg, but nonetheless a common positive association with older riverine OC. These findings reveal that a complex mixture of Hg sources, supplied across the MRB, will contribute to future trends in Hg export to the Arctic Ocean under rapid environmental changes.

The Abrolhos bank is home of the richest coral reef system of the Southwestern Atlantic, where endemic coral species are found. It has been reported that Abrolhos' corals are under intense stress due to increasing of Marine Heat Waves during the last decades. Additionally, anthropic interventions along the adjacent coastal regions are a factor of concern since they contribute to the increase in the sediment load and to organic debris input in the reef domain. In November 2015, the collapse of the Fundao mining tailings dam resulted in the release of approximately 50 million m3 of iron oxide and quartz-rich slurry into the Doce River. Aiming at using a fingerprint of the tailings and to assess the presence of traces of the Fundao dam material from this event on the Abrolhos bank, this work presents new 87Sr/86Sr and 143Nd/144Nd isotope ratios of marine suspended sediment samples collected between 2016 and 2020 from a network of sediment traps throughout the reef and complementary suspended material at sea. In parallel, we monitored meteo-oceanographic parameters and modeled surface marine currents as an attempt to identify the sediment transport between the Doce River mouth and Abrolhos bank. The r isotopes were used as provenance proxies based on the fact that minerals and rocks tend to have specific isotopic signatures reflecting their own geological derivation. In this context, the isotopic ratios of various potential regional sources for the sedimentation in Abrolhos bank were evaluated. Our monitoring and isotopic measurements indicate that Doce River signatures are detected at Abrolhos bank, following the seasonal Doce River discharge at sea. Isotopic signature of Doce River at Abrolhos bank was also observed during the austral winter (July–August) when cold fronts migrate at the Brazilian coast with higher frequency and energy.

Next to water quality deterioration, cyanobacteria blooms can affect turnover of aqueous carbon, including dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), and particulate organic carbon (POC). We investigated interactions of these three phases and their stable isotopes in a freshwater pond with periodic cyanobacterial blooms over a period of 23 months. This helped to map turnover and sources of aqueous carbon before, during, and after bloom events. During bloom events POC isotope values (δ13CPOC) increased up to −17.4‰, after aqueous CO2 (CO2(aq)) fell below an atmospheric equilibration value of 412 μatm. Additionally, carbon isotope enrichment between CO2(aq) and POC (eCO2-phyto) ranged from 2.0 to 21.5‰ with lowest fractionations observed at pH values above 8.9. The increase of δ13CPOC and decrease of eCO2-phyto values at low pCO2 and high pH was most likely caused by the activation of the carbon concentrating mechanism (CCM). This mechanism correlated with prevalent assimilation of 13C-enriched HCO3−. Surprisingly, CO2(aq) still contributed more than 50% to the POC pool down to pCO2 values of around 150 μatm. Only after this threshold the reduced eCO2-phyto suggested incorporation of 13C-enriched HCO3−.

Vegetable fields have a high risk of heavy metal contamination from pollution sources in suburban and industrial areas of cities. Eighty-seven soil samples, 106 leafy vegetables and 48 road dust samples were collected from industrial areas of Shanghai, China. We studied the levels of heavy metals, health risk through consumption of leafy vegetables, and sources of Pb in soils, road dust and leafy vegetables. Soil Cd, Zn, Pb, Cu, Hg and As concentrations exceeded the soil background values in 73.6%, 97.7%, 52.3%, 37.8%, 95.1% and 20.2% soil samples, respectively, but were below the criteria for agricultural soil in China, with the exception of Hg. The concentrations of Cd, Zn, Pb, Cu and As in road dust were significantly higher than concentrations in soils, while Hg concentration in road dust was lower. Cd, Zn, Pb, Hg and Cu concentrations in soils and Zn, Pb and Cu concentrations in road dust were greatest near the municipal solid waste incineration power plant. Heavy metal concentrations in the edible tissues of vegetables were not correlated with their total values in soils and varied among vegetable species. The trends in transfer factors (TFs) in different vegetables were Cd>Zn>Cu>As>Hg>Pb. There was low health risk from heavy metal exposure by consumption of vegetables based on Hazard Quotients (HQM): As was the major contributor to HQM, followed by Cd and Pb. Parent material of the Yangtze River Estuary was the major source of Pb in soils, while coal-fired, stationary industrial emissions and municipal waste incineration emissions were the major sources of Pb in dust and vegetables based on use of the lead isotopic tracing method. Accumulation of Pb in leafy vegetables was through foliar uptake and directly related to atmospheric Pb.

The Sulcis-Iglesiente district (SW Sardinia, Italy) has been, until recently, one of the most important Italian polymetallic mining areas for the extraction of lead. Epidemiological studies conducted over several decades have indicated this site at high risk of environmental crisis with possible adverse effects on the public health. In the present paper we discuss Pb isotope signatures in human scalp hair and road dust collected from the Sulcis-Iglesiente area in order to trace the exposure of populations to potential Pb sources. A total of 23 determinations (20 on hair samples and 3 on road dust samples) of lead isotope ratios (206Pb/207Pb and 208Pb/206Pb) were carried out. The obtained results were integrate with literature data regarding the total content of Pb in hair samples from the same study area. Hair from children living in Sant'Antioco exhibited lead isotope ratios in the ranges 1.152-1.165 for 206Pb/207Pb and 2.101-2.108 for 208Pb/206Pb, while hair samples from Iglesias resulted less radiogenic: 206Pb/207Pb~1.147-1.154 and 208Pb/206Pb~2.106-2.118. These values pointed to a multi-source mixing between the less radiogenic sources, corresponding to the Pb ore deposits, and the more radiogenic sources identified in local background.

Pyrene is a model contaminant of high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs), which are compounds that have potential carcinogenic effects and pose a serious threat to human health. Finding effective pyrene-degrading bacteria is crucial for removing PAHs from soil. In this study, DNA-based stable isotope probing (DNA-SIP) technology was used to investigate pyrene degraders in PAH-contaminated oilfield soil during natural attenuation (NA), bioaugmentation (BA) and biostimulation (BS). The results show that BA played an important role in pyrene degradation with the highest pyrene removal rate (~95%) after 12 days incubation, followed by removal rates of ~90% for NA and ~30% for BS. In addition, 6 novel pyrene degraders were identified, while 12 well-known PAH degraders were demonstrated to participate in the biodegradation of pyrene. Additionally, the external homologous strains introduced during BA promoted the degradation of pyrene, but not by directly participating in the metabolism of the target compound. Rhamnolipid supplementation during BS promoted the involvement of more microorganisms in the degradation of pyrene, which was beneficial to identifying more pyrene degraders via DNA-SIP. These findings provide new insight into the effects of external homologous strains and supplementary rhamnolipids on pyrene degradation.

The Bikar and Bokak Atolls, located in the northern Marshall Islands, are extremely isolated and consist of pristine marine and terrestrial ecosystems. Both atolls may have experienced significant radioactive deposition following the nuclear weapon testing conducted at Bikini and Enewetak proving grounds. Here we report activity concentrations of artificial radionuclides (239Pu, 240Pu, 241Pu, 241Am, 137Cs and 90Sr) in marine and terrestrial samples collected from Bikar and Bokak Atolls. Artificial radionuclides in soil from the Majuro Atoll are also reported and form a radiological baseline against which the levels at the other atolls can be compared. We observed low levels of artificial radionuclides in soil from Majuro and Bokak, but significantly higher levels in soil from Bikar. The residual radioactivity in the Bikar environment is comparable to the levels previously reported for other nearby atolls, including Taka and Utrik, but lower than for Rongerik, Rongelap, Bikini and Enewetak. An analysis of 240Pu/239Pu isotope ratios and estimations of the dates of contamination from 241Am/241Pu activity ratios both indicated that the Bikar Atoll was contaminated mainly by radioactive fallout from the Castle Bravo test in 1954. We compare the results of our measurements at Bikar and Bokak to data from other atolls in the Marshall Islands and to regions of the world affected by both global and regional fallout from atmospheric nuclear weapons testing and nuclear accidents.

Understanding interactions between surface water (SW) and groundwater (GW) is challenging because of the lack of information available and the complexity of the processes involved. In this paper, SW-GW interactions are simulated using numerical modelling integrated with insights from water isotopes. Isotope analysis can be used to (i) determine the relative contribution from different sources of water into aquifer recharge and (ii) identify areas with high SW-GW interactions. The results, for the Shiraz catchment in Iran, show that (i) SWAT-MODFLOW has better performance than stand-alone SWAT (R2 improvement from 0.50 to 0.54) and (ii) SWAT-MODFLOW calibrated with insights from isotope data (SWAT-MODFLOW-ISO) has significantly better performance than SWAT-MODFLOW (R2 improvement from 0.54 to 0.68 and RMSE reduction from 1.67 to 1.33). This demonstrates that insights into SW-GW interactions that are revealed by isotopes can be used to improve hydrological modelling performance.

Studies of plant water sources generally assume that xylem water integrates the isotopic composition (δ2H and δ18O) of water sources and does not fractionate during uptake or transport along the transpiration pathway. However, woody xerophytes, halophytes, and trees in mesic environments can show isotopic fractionation from source waters. Isotopic fractionation and variation in isotope composition can affect the interpretation of tree water sources, but most studies to date have been greenhouse experiments. Here we present a field-based forensic analysis of xylem water isotope composition for 12 Eucalyptus tetrodonta and Corymbia nesophila trees. We used a 25-tonne excavator to access materials from the trees' maximum rooting depth of 3 m to their highest canopies at 38 m. Substantial within-tree variation occurred in δ2H (−91.1‰ to −35.7‰ E. tetrodonta; −88.8‰ to −24.5‰ C. nesophila) and δ18O (−12.3‰ to −5.0‰ E. tetrodonta; −10.9‰ to −0.3‰ C. nesophila), with different root-to-branch isotope patterns in each species. Soil water δ2H and δ18O dual isotope slopes (7.26 E. tetrodonta, 6.66 C. nesophila) were closest to the Local Meteoric Water Line (8.4). The dual isotope slopes of the trees decreased progressively from roots (6.45 E. tetrodonta, 6.07 C. nesophila), to stems (4.61 E. tetrodonta, 5.97 C. nesophila) and branches (4.68 E. tetrodonta, 5.67 C. nesophila), indicative of fractionation along the xylem stream. Roots of both species were more enriched in 2H and 18O than soil water at all sampled depths. Bayesian mixing model analysis showed that estimated proportions of water sourced from different depths reflected the contrasting root systems of these species. Our study adds evidence of isotopic fractionation from water uptake and along the transpiration stream in mature trees in monsoonal environments, affecting the interpretation of water sources. We discuss the findings with view of interpreting aboveground xylem water isotopic composition, incorporating knowledge of root systems.

In order to trace the sources of sediment materials and trace metals in the Weser River system (Germany), and the riverine input to the North Sea, Sr, Nd and Pb isotopes, together with multi-elemental compositions, were measured for sediments collected over the entire Weser River Basin, from headwaters to the estuary. Mass fractions of metals, including Ag, Cd, and Pb, and of one metalloid, Sb, higher than their crustal abundance, were observed within the entire Weser Basin. Isotope-amount ratio n(87Sr)/n(86Sr) and εNd ranged from 0.71182 ± 0.00005 to 0.72880 ± 0.00009 and −11.3 ± 0.3 to −21.0 ± 0.3, respectively. n(206Pb)/n(204Pb), n(207Pb)/n(204Pb), and n(208Pb)/n(204Pb) ranged from 18.226 ± 0.008 to 18.703 ± 0.012, 15.613 ± 0.007 to 15.653 ± 0.012 and 38.14 ± 0.02 to 38.84 ± 0.02, respectively. Sr and Nd isotope compositions reflected primarily a mixture of natural materials derived from the Weser Basin. Pb isotope signatures indicated strong anthropogenic influences in the middle-lower Weser region. Pb isotopic compositions in the sediments from the Aller (tributary of the Weser) and its tributary suggested influence from historical Pb-Zn ore mining in the Harz Mountains that might contribute to the observed elevated mass fractions of Ag, Cd, Sb and Pb in that region. K-means cluster and principal component analysis of the Sr, Nd, and Pb isotope data yielded results consistent with their isotope systematics, supporting statistical analysis as an unsupervised tool in isotope fingerprinting studies. Sr, Nd, and Pb isotopic signatures in the sediments of the Weser were distinctively different from those of another major river discharging into the North Sea, the Elbe. This suggested that this Sr, Nd, and Pb isotope dataset can be used to distinguish riverine input of sediment materials and metals between the two rivers, thereby assessing their individual contribution to materials transported into the North Sea.

Both natural processes and anthropogenic activities have significant effects on groundwater evolution in coal mining regions. In this study, the primary controlling mechanism of the groundwater chemistry evolution for the Carboniferous groundwater in the Huaibei coalfield, North China was proposed based on the hydrogeochemical indicators combining with multiple isotope tracers. The diversity of hydrochemical types indicates the complexity of the hydrogeochemical environment in the groundwater, which is recharged by precipitation infiltration with minimal evaporation according to the distributions of δD and δ18O. Additionally, ion correlation analysis suggests that minerals dissolution and cation exchange between Na+ and Ca2+ are the dominant processes within that groundwater. The hydrochemical and δ13CDIC characteristics of the groundwater demonstrate that HCO3− is mainly controlled by the dissolution of carbonate minerals and soil CO2, and the proportion of the latter is believed to be dominated by the hydrogeologic conditions. Similarly, the values of SO42− and δ34SSO4 indicate that a small portion of SO42− in the groundwater in the northern part originates from the meteoric precipitation, while it is mainly derived from the dissolution of gypsum in the southern part. Furthermore, mining activities also alter the groundwater level and flow conditions through pumping and drainage, which enhances the interaction between groundwater and aquifer lithologies, thereby affects the hydrogeochemical processes. The findings of this work are of great significance for promoting the safe exploitation of deep coal resources and the sustainable utilization of groundwater in the Huaibei coalfield, as well as the most of other coalfields in North China.

Water is a limiting factor and significant driving force for ecosystem processes in arid and semi-arid areas. Knowledge of plant water uptake pattern is indispensable for understanding soil-plant interactions and species coexistence. The 'Grain for Green' project that started in 1999 in the Loess Plateau of China has led to large scale vegetation change. However, little is known about the water uptake patterns of the main plant species that inhabit in this region. In this study, the seasonal variations in water uptake patterns of three representative plant species, Stipa bungeana, Artemisia gmelinii and Vitex negundo, that are widely distributed in the semi-arid area of the Loess Plateau, were identified by using dual stable isotopes of δ2H and δ18O in plant and soil water coupled with a Bayesian mixing model MixSIAR. The soil water at the 0-120cm depth contributed 79.54±6.05% and 79.94±8.81% of the total water uptake of S. bungeana and A. gmelinii, respectively, in the growing season. The 0-40cm soil contributed the most water in July (74.20±15.20%), and the largest proportion of water (33.10±15.20%) was derived from 120-300cm soils in August for A. gmelinii. However, V. negundo obtained water predominantly from surface soil horizons (0-40cm) and then switched to deep soil layers (120-300cm) as the season progressed. This suggested that V. negundo has a greater degree of ecological plasticity as it could explore water sources from deeper soils as the water stress increased. This capacity can mainly be attributed to its functionally dimorphic root system. V. negundo may have a competitive advantage when encountering short-term drought. The ecological plasticity of plant water use needs to be considered in plant species selection and ecological management and restoration of the arid and semi-arid ecosystems in the Loess Plateau.

In this study, we used stable isotope-labeled soluble microbial products (SMP) and substrates to explore their assimilation into the formation of new biological products (i.e., extracellular polymeric substances and biomass) in two adjacent sequencing batch reactors. The isotope labeling approach along with fluorescence spectroscopy allowed us to distinguish between refractory and labile portions of SMP constituents as well as their roles in the formation of extracellular polymeric substances (EPS). Comparison of SMP fluorescence and the specific UV absorbance values between the two reactors revealed the presence of humic-like aromatic substances in the non-consumable part of SMP, which can be ultimately released as effluent organic matter. Parallel factor analysis modeling of fluorescence spectra showed that the hydrolysis of EPS contents mostly resulted in humic-like components in SMP rather than protein-like components, which were initially abundant in EPS (>80%). From variations in carbon and nitrogen isotopic contents in EPS and biomass, it was found that carbon-containing substrates were enriched faster than their nitrogenous counterparts. The contributions to new EPS formation reached 87.5% for carbon and 60.5% for nitrogen. Meanwhile, the isotopic tracking of the labeled SMP revealed that only 11.0% and 11.9% of carbon and 13.3% and 11.6% of nitrogen from the influent SMP were finally assimilated into EPS and biomass, respectively. In contrast, the isotopic enrichment in SMP was higher (~50%) than that of EPS and biomass, indicating the low bioavailability and refractory nature of the feed SMP. This study proposed a promising approach for estimating the relative contributions of different forms of labile substrate and SMP to the formation of EPS in activated sludge processes. This approach could be suggested as a versatile method for establishing the kinetics, substrate element flow, mass balance on organic substrates and nutrients, as well as for tracking the consumption and uptake pathways of hazardous materials.