Isotopic,Geochemical and Biological Tracing of the Source of an Impacted Karst Spring,Weldon Spring,Missouri

Weldon Spring is consistently enriched in¹⁸O relative to other karst springs in east-central Missouri and western Illinois, suggesting an evaporated source component. Regional potentiometric head maps of the shallow aquifer suggest that Prairie Lake, an artificial lake built between 1954 and 1982, could represent this component. Isotopic, biological and chemical tracing of the spring conclusively verify the hypothesis that this lake has impacted Weldon Spring. Mixing calculations indicate that Weldon Spring is now comprised of approximately 80% lake water and 20% groundwater. Recent measurements indicate that the discharge rate of the spring is now approximately 10 times the rate prior to the construction of the lake, confirming the augmentation of flow by a new source. Analysis of the isotopic trends indicates that the subsurface travel time is short, and suggests that the conduits connecting the lake and the spring may be progressively enlarging.     

The Use of the Isotopic Composition of Individual Compounds for Correlating Spilled Oils and Refined Products in the Environment with Suspected Sources

Correlation of crude oils, or refined products, in the environment with suspected sources is typically undertaken through the use of GC and GCMS and in certain cases bulk carbon isotope compositions. However, with crude condensates, or refined products in particular, the absence, or low concentration, of biomarkers precludes their successful use for making unique correlations. An alternative and, sometimes, complimentary technique for correlation of such products is evolving through the use of combined gas chromatography-isotope ratio mass spectrometry (GCIRMS). This approach permits determination of the carbon and hydrogen isotopic composition of individual compounds in the crude oil or refined product to produce isotopic fingerprints for use in correlation studies. In this paper, it is proposed to review applications of GCIRMS to the correlation of various spilled products with their suspected sources in different environments. Whilst not proposing that this technique will replace GC or GCMS; it is proposed that GCIRMS is a very powerful tool to be used in conjunction with GC and GCMS to make such correlations. Although isotopic fractionation has been observed in some of the lighter components such as benzene and toluene, higher carbon numbered compounds, say above C 10 , do not appear to undergo any significant isotopic fractionation as a result of weathering. Furthermore with refined products, isotopic fractionation of the lighter components has the potential to demonstrate the onset of natural attenuation of refined products in the environment.     

Elements Influencing Cost Allocation in the Pinal Creek Aquifer,Arizona, USA. Part I: Geochemical Fingerprinting and Source Delineation

This is the first in a three-article series in this volume of Environmental Forensics describing the framework that was developed to quantitatively allocate mass loading of metals to the Pinal Creek alluvial aquifer. This article describes geochemical fingerprinting, followed by spatial and temporal analysis of Pinal Creek monitoring well data (more than 600,000 records from hundreds of locations), which identified three distinct source areas and plumes on the basis of facility-specific differences in process geochemistry, ore mineralogy, and solution handling. The primary Webster Lake/Gulch source originated in 1926 (700 mg/L chlorine, 200 mg/L copper, 3000–9000 mg/L iron). Secondary contributions from the Bluebird/Oxhide/Live Oak Gulch/Davis Canyon leach complex in Upper Bloody Tanks Wash began circa 1962 (30–200 mg/L chlorine, 1500–3500 mg/L copper, <500 mg/L iron), and recent (1992–2001) contributions came from Miami Unit hydromining releases to Bloody Tanks Wash (30–70 mg/L chlorine, ～1000 mg/L copper, ～2000 mg/L iron). In Kiser Basin, where the plumes commingle, temporal evolution of the plume chemistry is reflected in a shift from a predominantly iron:copper-rich solution (10:1) to an increasingly copper-dominated signature (1:1) with the arrival of the secondary plume. Based on historical records and geochemical fingerprints, the original acid front migrated through the alluvium at ～0.5 m/day; however, later acidic releases traveled at ～2.3 m/day due to exhaustion of the available buffering capacity. The divisible nature of the plume supports quantitative allocation of contributions to the aquifer.     

Distribution and sources of polycyclic aromatic hydrocarbons in surface sediments of rivers and an estuary in Shanghai, China

Concentrations, spatial distribution and sources of 17 polycyclic aromatic hydrocarbons (PAHs) and methylnaphthalene were investigated in surface sediments of rivers and an estuary in Shanghai, China. Total PAH concentrations, excluding perylene, ranged from 107 to 1707 ng/g-dw. Sedimentary PAH concentrations of the Huangpu River were higher than those of the Yangtze Estuary. The concentration of the Suzhou River was close to the average concentration of the Huangpu River. PAHs source analysis suggested that, in the Yangtze Estuary, PAHs at locations far away from cities were mainly from petrogenic sources. At other locations, both petrogenic and pyrogenic inputs were significant. In the Huangpu and Suzhou Rivers, pyrogenic input outweighed other sources. The pyrogenic PAHs in the upper reaches of the Huangpu River were mainly from the incomplete combustion of grass, wood and coal, and those in the middle and lower reaches were from vehicle and vessel exhaust.     

Combined effects of deltamethrin, temperature and salinity on oxidative stress biomarkers and acetylcholinesterase activity in the black tiger shrimp (Penaeus monodon)

This study aimed to investigate the interactions of two abiotic factors (temperature and salinity) and deltamethrin (pyrethroid pesticide) exposure on some oxidative stress biomarkers as well as on acetylcholinesterase activity (AChE) in hepatopancreas, gills and muscle of black tiger shrimp (Penaeus monodon). A combination of three temperatures (24, 29 and 34 °C), two salinities (15 and 25 ppt), and the absence or presence of 0.1 μg L⁻¹ deltamethrin was applied on shrimp during 4 d under laboratory conditions. Lipid peroxidation level (LPO) and glutathione S-transferase activity (GST) were not affected by combined effect of temperature, salinity and deltamethrin in any of the studied tissues. Deltamethrin impaired other tested oxidative stress biomarkers, i.e. total glutathione (tGSH), catalase (CAT), glutathione peroxidase (GPx). tGSH level significantly increased in hepatopancreas due to deltamethrin exposure mainly at 34 °C, while pesticide effects on tGSH and CAT activity in gills were influenced by both temperature and salinity. In addition, GPx activity in hepatopancreas decreased after deltamethrin treatment mainly at 24 °C. Finally, AChE in muscle was strongly inhibited by deltamethrin at all tested temperatures and salinities. These novel findings demonstrate that interactions between abiotic factors and a commonly used pesticide exposure should be taken into account when analyzing some widespread biomarkers in black tiger shrimp.     

Interactions of Physical, Chemical, and Biological Weather Calling for an Integrated Approach to Assessment, Forecasting, and Communication of Air Quality

This article reviews interactions and health impacts of physical, chemical, and biological weather. Interactions and synergistic effects between the three types of weather call for integrated assessment, forecasting, and communication of air quality. Today’s air quality legislation falls short of addressing air quality degradation by biological weather, despite increasing evidence for the feasibility of both mitigation and adaptation policy options. In comparison with the existing capabilities for physical and chemical weather, the monitoring of biological weather is lacking stable operational agreements and resources. Furthermore, integrated effects of physical, chemical, and biological weather suggest a critical review of air quality management practices. Additional research is required to improve the coupled modeling of physical, chemical, and biological weather as well as the assessment and communication of integrated air quality. Findings from several recent COST Actions underline the importance of an increased dialog between scientists from the fields of meteorology, air quality, aerobiology, health, and policy makers.     

Determination of organochlorine pesticide residue in sediment and water from the Densu river basin, Ghana

The distribution of organochlorine pesticides in the aquatic ecosystem from the Densu river revealed varying levels of concentration in water and the sediment samples. Three locations were sampled along the river to evaluate the levels of organochlorine pesticide residue in the river. Sediment and surface water samples were extracted by soxhlet and liquid-liquid extraction respectively and analyzed using Gas Chromatograph coupled with electron capture detector. The detectable organochlorine pesticides were gamma-hexachlorocyclohexane (HCH), delta-hexachlorocyclohexane, heptachlor, aldrin and dieldrin. The other pesticides that were investigated are gamma-chlordane, alpha endosulfan, endosulfan sulfate, p,p′-DDT and its metabolite p,p′-DDE, methoxychlor, endrin and its metabolite endrin aldehyde and endrin ketone. The order of increasing frequency of detection of samples was higher in sediment than water. In sediment, the mean concentration ranged from 0.030 μg kg⁻¹ dry weight (endrin) to 10.98 μg kg⁻¹ dry weight (aldrin). The highest detected concentration of organochlorine in water was endosulfan sulfate with mean concentration of 0.185 μg L⁻¹. Analysis of variance indicated significant differences for most organochlorine pesticide residue in the sediment sampled from the various locations. Some of the levels of organochlorine pesticides detected in water were relatively high compared to guideline values set by World Health Organization and Australia and thus could be harmful if the trend is not checked.     

Testing the Established Hydrogeologic Model of Source Water to the Amargosa River Basin,Inyo and San Bernardino Counties,California

The current conceptual hydrogeologic model established for source water to the Amargosa River was tested in order to help inform management decisions regarding the Amargosa River's Federal designation as Wild and Scenic through an Act of Congress. The limited availability of water in this region results in the critical need for effective management in the basin to maintain its Wild and Scenic attributes inclusive of habitat for several endangered and threatened species. The use of forensic tools and integration of multiple lines of geologic, hydrogeologic, geochemical, and stable isotopic evidence suggest that the simple historical model for primary groundwater transport through this region is incorrect and that a large supply of regional baseflow does not provide the hydrogeological foundation of the Amargosa River basin. Data collected is consistent with an alternative model requiring complex source mixing and shallow alluvial groundwater that supports river flow. This conclusion also suggests Wild and Scenic conditions in this basin are more precarious than previously understood.     

Characterization of flow and transport processes within the unsaturated zone of Yucca Mountain, Nevada, under current and future climates

This paper presents a large-scale modeling study characterizing fluid flow and tracer transport in the unsaturated zone of Yucca Mountain, Nevada, a potential repository site for storing high-level radioactive waste. The study has been conducted using a three-dimensional numerical model, which incorporates a wide variety of field data and takes into account the coupled processes of flow and transport in the highly heterogeneous, unsaturated fractured porous rock. The modeling approach is based on a dual-continuum formulation of coupled multiphase fluid and tracer transport through fractured porous rock. Various scenarios of current and future climate conditions and their effects on the unsaturated zone are evaluated to aid in the assessment of the proposed repository's system performance using different conceptual models. These models are calibrated against field-measured data. Model-predicted flow and transport processes under current and future climates are discussed.     

Combination of in vitro bioassays for the determination of cytotoxic and genotoxic potential of wastewater, surface water and drinking water samples

In this study we evaluated genotoxicity and cytotoxicity of native samples of wastewaters (15 samples), surface waters (28 samples) and potable waters (8 samples) with the SOS/umuC assay with Salmonella typhimurium TA1535/pSK1002 and MTT assay with human hepatoma HepG2 cells. The genotoxicity of selected samples was confirmed with the comet assay with HepG2 cells. In the SOS/umuC assay 13 out of the 51 samples were genotoxic: two effluent samples from chemical industry; one sample of wastewater treatment plant effluent; two hospital wastewater samples; three river water samples and four lake water samples. Six samples were cytotoxic for HepG2 cells: both effluent samples of chemical industry, two wastewater treatment plant effluent samples, and two river water samples, however, only the chemical industry effluent samples were genotoxic and cytotoxic, indicating that different contaminants are responsible for genotoxic and toxic effects. Comparing genotoxicity of river and lake water samples with the chemical analytical data of the presence of the residues of pharmaceutical and personal care products (non-steroidal anti-inflammatory drugs, UV filters and disinfectants) in these samples, indicated that the presence of UV filters might be linked to the genotoxicity of these samples. The results showed that the application of the bacterial SOS/umuC assay and mammalian cell assays (MTT and comet assay) with HepG2 cells was suitably sensitive combination of assays to monitor genotoxicity and cytotoxicity of native samples of wastewaters and surface waters. With this study we also confirmed that the toxicity/genotoxicity bioassays should be an integral tool in the evaluation of toxicity of complex wastewaters before the release into environment, as well as for the monitoring of surface water quality, providing data useful in risk assessment.     

Source Type Evaluation of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Sediments from the Muar River and Pulau Merambong,Peninsular Malaysia

This article is the most recent report of polycyclic aromatic hydrocarbons (PAHs) in the Muar River and Pulau Merambong, Peninsular Malaysia. A total of 16 priority pollutant PAHs in addition to methylphenanthrene among alkylated PAHs were analyzed in surface sediments during May 2013. Total PAHs ranged from 212 to 440 and 151 to 412 ng g^?1 dw in sediments from the Muar River and the Pulau Merambong, respectively. The Muar River showed an increasing trend of PAH concentrations, while no previous data exist for the Pulau Merambong. Generally, mixed petrogenic and pyrogenic sources of PAHs with predominance of the latter were detected in the study area. Effective management of oil pollution has caused a drastic decrease in petrogenic sources of PAHs.     

Determination of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in surface waters from the Haihe River in Tianjin by gas chromatography-mass spectrometry with selected ion monitoring

The estrogenic pollutants 4-tert-octylphenol (OP), 4-nonylphenol (NP) and bisphenol A (BPA) were determined in surface water samples from the Haihe River, Tianjin, China. The analytes were extracted and concentrated from 300 ml acidified water samples by liquid–liquid extractions using dichloromethane, derivatized with trifluoroacetic anhydride, and quantified by gas chromatography–mass spectrometry (GC–MS) with selected ion monitoring (SIM). Among the samples collected from 14 sampling sites, only one sample was found to have a relatively high concentration of BPA (8.30 μg l⁻¹) and NP (0.55 μg l⁻¹). The concentrations of OP, NP and BPA in the other samples were in the range of 18.0–20.2, 106–296 and 19.1–106 ng l⁻¹, respectively. Recoveries for OP, NP and BPA in the spiked water samples were all over 80%.     

Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem

Our objective was to examine how the behavior of atmospheric mercury (Hg) deposited to boreal lake mesocosms changed over time. We added inorganic Hg enriched in a different stable isotope in each of two years, which allowed us to differentiate between Hg added in the first and second year. Although inorganic Hg and methylmercury (MeHg) continued to accumulate in sediments throughout the experiment, the availability of MeHg to the food web declined within one year. This decrease was detected in periphyton, zooplankton, and water mites, but not in gomphid larvae, amphipods, or fish. We suggest that reductions in atmospheric Hg deposition should lead to decreases in MeHg concentrations in biota, but that changes will be more easily detected in short-lived pelagic species than long-lived species associated with benthic food webs.     

The dispersal and storage of sediment-associated metals in an arid river system: the Leichhardt River, Mount Isa, Queensland, Australia

This paper details the distribution of Cu, Pb and Zn in aquatic systems draining Mount Isa Ag-Cu-Pb-Zn Mine in arid northern Queensland, Australia. Sediment-metal concentrations in the <2mm grain-size fraction adjacent to and downstream of the mine significantly exceed background concentrations (Cu, 159; Pb, 36; Zn, 86 ppm) as well as Australian government sediment quality low trigger guidelines (Cu, 65; Pb, 50; Zn, 200 ppm). Overbank sediments are more contaminated than channel sediments with mean values of Cu, 480; Pb, 540; Zn, 750 ppm. Mean concentrations in cut riverbank samples from the <2mm fraction were Cu, 195; Pb, 724; Zn, 807 ppm. Corresponding <180 microm samples returned concentrations of Cu, 321; Pb, 995; Zn, 1110 ppm. Delivery of contaminants during wet seasons from Mount Isa Mine and historically contaminated riverbanks remains an ongoing issue. The ease of dust entrainment in arid zones means that sediments enriched in toxic concentrations of metals may be widely dispersed and ultimately ingested and absorbed by biota.     

Bacteria, hypertolerant to arsenic in the rocks of an ancient gold mine, and their potential role in dissemination of arsenic pollution

The aim of the present study was to find out if bacteria present in ancient gold mine could transform immobilized arsenic into its mobile form and increase its dissemination in the environment. Twenty-two arsenic-hypertolerant cultivable bacterial strains were isolated. No chemolithoautotrophs, which could use arsenite as an electron donor as well as arsenate as an electron acceptor, were identified. Five isolates exhibited hypertolerance to arsenic: up to 500 mM of arsenate. A correlation between the presence of siderophores and high resistance to arsenic was found. The results of this study show that detoxification processes based on arsenate reductase activity might be significant in dissemination of arsenic pollution. It was concluded that the activity of the described heterotrophic bacteria contributes to the mobilization of arsenic in the more toxic As(III) form and a new mechanism of arsenic mobilization from a scorodite was proposed.     

Pollutants and the health of green sea turtles resident to an urbanized estuary in San Diego, CA

Rapid expansion of coastal anthropogenic development means that critical foraging and developmental habitats often occur near highly polluted and urbanized environments. Although coastal contamination is widespread, the impact this has on long-lived vertebrates like the green turtle (Chelonia mydas) is unclear because traditional experimental methods cannot be applied. We coupled minimally invasive sampling techniques with health assessments to quantify contaminant patterns in a population of green turtles resident to San Diego Bay, CA, a highly urbanized and contaminated estuary. Several chemicals were correlated with turtle size, suggesting possible differences in physiological processes or habitat utilization between life stages. With the exception of mercury, higher concentrations of carapace metals as well as 4,4′-dichlorodiphenyldichloroethylene (DDE) and γ chlordane in blood plasma relative to other sea turtle studies raises important questions about the chemical risks to turtles resident to San Diego Bay. Mercury concentrations exceeded immune function no-effects thresholds and increased carapace metal loads were correlated with higher levels of multiple health markers. These results indicate immunological and physiological effects studies are needed in this population. Our results give insight into the potential conservation risk contaminants pose to sea turtles inhabiting this contaminated coastal habitat, and highlight the need to better manage and mitigate contaminant exposure in San Diego Bay.     

Application of an ELISA to the quantification of carbamazepine in ground, surface and wastewaters and validation with LC-MS/MS

Carbamazepine is a psychiatric pharmaceutical widely detected in aquatic environments. Due to its generalized occurrence and environmental persistence it might be considered as an anthropogenic pollution indicator. In this research, a previously developed enzyme-linked immunosorbent assay (ELISA), based on a commercial monoclonal antibody, was applied to the quantification of carbamazepine in ground, surface and wastewaters and results were validated by liquid chromatography-tandem mass spectrometry (LC-MS/MS).The performance of the applied ELISA methodology was tested in the presence of high concentrations of sodium chloride and dissolved organic matter. The method was not significantly affected by matrix effects, being adequate for the quantification of carbamazepine in environmental samples, even without sample pre-treatment. This method allows the quantification of carbamazepine in the range of 0.03-10 μg L⁻¹, with a relative error lower than 30%. Due to a pH dependent cross-reactivity with cetirizine, an antihistaminic drug, the assay also enabled the quantification of cetirizine in the samples.The application of the developed method to the quantification of carbamazepine was performed by using environmental samples with very different matrices, collected in the geographical area of Ria de Aveiro, an estuarine system located in the North of Portugal. Carbamazepine was detected in all analyzed wastewater samples and in one surface water with concentrations between 0.1 and 0.7 μg L⁻¹. Validation with LC-MS/MS revealed that results obtained by ELISA are 2-28% overestimated, which was considered highly satisfactory due to the absence of sample pre-treatments.     

Development and field validation of an indicator to assess the relative mobility and risk of pesticides in the Lourens River catchment,South Africa

A GIS based pesticide risk indicator that integrates exposure variables (i.e. pesticide application, geographic, physicochemical and crop data) and toxicity endpoints (using species sensitivity distributions) was developed to estimate the Predicted Relative Exposure (PREX) and Predicted Relative Risk (PRRI) of applied pesticides to aquatic ecosystem health in the Lourens River catchment, Western Cape, South Africa. Samples were collected weekly at five sites from the beginning of the spraying season (October) till the beginning of the rainy season (April) and were semi quantitatively analysed for relevant pesticides applied according to the local farmers spraying programme. Monitoring data indicate that physicochemical data obtained from international databases are reliable indicators of pesticide behaviour in the Western Cape of South Africa. Sensitivity analysis identified K_OC as the most important parameter influencing predictions of pesticide loading derived from runoff. A comparison to monitoring data showed that the PREX successfully identified hotspot sites, gave a reasonable estimation of the relative contamination potential of different pesticides at a site and identified important routes of exposure (i.e. runoff or spray drift) of different pesticides at different sites. All pesticides detected during a monitored runoff event, were indicated as being more associated with runoff than spray drift by the PREX. The PRRI identified azinphos-methyl and chlorpyrifos as high risk pesticides towards the aquatic ecosystem. These results contribute to providing increased confidence in the use of risk indicator applications and, in particular, could lead to improved utilisation of limited resources for monitoring and management in resource constrained countries.     

Polycyclic aromatic hydrocarbon (PAH) deposition to and exchange at the air-water interface of Luhu, an urban lake in Guangzhou, China

Urban lakes are vulnerable to the accumulation of semivolatile organic compounds, such as PAHs from wet and dry atmospheric deposition. Little was reported on the seasonal patterns of atmospheric deposition of PAHs under Asian monsoon climate. Bulk (dry + wet) particle deposition, air-water diffusion exchange, and vapour wet deposition of PAHs in a small urban lake in Guangzhou were estimated based on a year-round monitoring. The total PAH particle deposition fluxes observed were 0.44-3.46 μg m⁻² day⁻¹. The mean air-water diffusive exchange flux was 20.7 μg m⁻² day⁻¹. The vapour deposition fluxes of PAHs ranged 0.15-8.26 μg m⁻² day⁻¹. Remarkable seasonal variations of particulate PAH deposition, air-water exchange fluxes and vapour wet deposition were influenced by seasonal changes in meteorological parameters. The deposition fluxes were predominantly controlled by the precipitation intensity in wet season whereas by atmospheric concentration in dry season.