Gull-derived trace elements trigger small-scale contamination in a remote Mediterranean nature reserve

The role of a yellow-legged gull (Larus michahellis) small colony in conveying trace elements (As, Cd, Cr, Cu, Ni, Pb, THg, V, Zn) was assessed in a Mediterranean nature reserve (Marinello ponds) at various spatial and temporal scales. Trace element concentrations in guano were high and seasonally variable. In contrast, contamination in the ponds was not influenced by season but showed strong spatial variability among ponds, according to the different guano input. Biogenic enrichment factor B confirmed the role of gulls in the release of trace elements through guano subsidies. In addition, comparing trace element pond concentrations to the US NOAA’s SQGs, As, Cu and Ni showed contamination levels associated with possible negative biological effects. Thus, this study reflects the need to take seabirds into account as key factors influencing ecological processes and contamination levels even in remote areas, especially around the Mediterranean, where these birds are abundant but overlooked.     

Hydrochemical and Multivariate Statistical Evaluation of Heavy Metals in Shallow Alluvial Aquifers of North Brahmaputra Plain,India

The aim of this study was to display distribution and relationships of heavy elements in the unconfined, shallow alluvial aquifers of the lower Jia Bharali catchment and adjoining areas in central part of North Brahmaputra Plain (NBP), India using hydrochemical as well as multivariate statistical techniques such as principal component analysis (PCA) and cluster analysis. The original matrix was made up of 10 trace elements (As, Cd, Cu, Co, Cr, Fe, Mn, Pb, Ni and Zn) estimated from 50 shallow alluvial dug wells in both the wet and the dry season for a duration of 3 hydrological years (2008–2011). Except As, Cu and Zn all the other toxic metals in the shallow aquifers were found exceeding the WHO maximum permissible limits for drinking water. PCA extracted five varimax factors as geogenic, agricultural and anthropogenic explaining about 71.2% of the total variance in the wet season and 69.3% total variance in the dry season. Hierarchical cluster analysis classified the dug wells into two groups in the wet season and three groups in the dry season with respect to the heavy elements. The results emphasized the need for routine monitoring and management in order to avoid contamination of groundwater sources in the NBP with respect to the dissolved trace elements.     

Study of the spatial and historical distribution of sediment inorganic contamination in the Toulon bay (France)

This study presents trace elements levels in surface and deep sediments of the Toulon bay (SE France) subjected to anthropogenic inputs (navy base, harbors, etc.). The studied elements (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) are defined as priority contaminants in aquatic systems. Fifty-five points scattered on the entire bay were sampled, allowing the determination of contaminants distribution with a high resolution. Several approaches were used to assess the degree of contamination and the potential toxicity of the Toulon bay sediments: comparison to the French legislation, surface-weighted average metal concentrations, enrichment factors (EF), geoaccumulation indices (Igeo), trace element stock calculation and comparison to sediment quality guidelines. A principal component analysis was performed to reveal common behavior of the studied contaminants. Results demonstrated the very high contamination of the small bay, especially in Hg (EF up to 1500), Cu, Pb and Zn, with export to the large bay further governed by hydrodynamics.     

Groundwater Pumping Is a Significant Unrecognized Contributor to Global Anthropogenic Element Cycles

Quantifying anthropogenic contributions to elemental cycles provides useful information regarding the flow of elements important to industrial and agricultural development and is key to understanding the environmental impacts of human activity. In particular, when anthropogenic fluxes reach levels large enough to influence an element's overall cycle the risk of adverse environmental impacts rises. While intensive groundwater pumping has been observed to affect a wide-range of environmental processes, the role of intensive groundwater extraction on global anthropogenic element cycles has not yet been characterized. Relying on comprehensive datasets of groundwater and produced water (groundwater pumped during oil/gas extraction) chemistry from the U.S. Geological Survey along with estimates of global groundwater usage, I estimate elemental fluxes from global pumping, consumptive use, and depletion of groundwater. I find that groundwater fluxes appreciably contribute to a number of elements overall cycles and thus these cycles were underestimated in prior studies, which did not recognize groundwater pumping's role. I also estimate elemental loadings to agricultural soils in the United States and find that in some regions, groundwater may provide a significant portion (more than 10%) of crop requirements of key nutrients (K, N). With nearly 40% of globally irrigated land under groundwater irrigation, characterizing nutrient and toxic element fluxes to these soils, which ultimately influence crop yields, is important to our understanding of agricultural production. Thus, this study improves our basic understanding of anthropogenic elemental cycles and demonstrates that quantification of groundwater pumping elemental fluxes provides valuable information about the potential for environmental impacts from groundwater pumping.     

Assessment of Groundwater Quality at Yuncheng Basin: Denotation for the Water Management in China

Dramatic decreases in groundwater quality have raised widespread concerns about water supplies and ecological crises in China. In this study, hydrochemistry, stable isotopes, and graphical and multivariate statistical methods are integrated to identify hydrogeochemical processes controlling groundwater quality in the Yuncheng Basin, China. Our results show that groundwater with 21 variables (pH, temperature-T, total dissolved solid, major-trace elements, and stable isotopes) is chemically classified into three distinct clusters: fresh water [C1], brackish-saline water [C2], and saline water [C3]. Groundwater salinization is identified as the prime process in controlling groundwater quality for shallow groundwater and deep groundwater in the lowland areas. Large-scale As, F, or B contaminations found in groundwater are closely related to groundwater salinization, agricultural activity, and the exploration of geothermal water in the area. With respect to the risk of contamination, groundwater in the basin is spatially divided into the following: shallow groundwater with a high risk located in the north side of the Salt Lake, shallow groundwater with a moderate risk, and deep groundwater with a low to moderate risk. Nationally, the increasing demand on groundwater is threatened by a range of environmental and health pressures, including salinization and contaminations of nitrate, As, F, or B. Our study indicates that natural water-rock interactions and hydrogeological conditions are significant factors controlling these contaminations. Systematic management and regulation of existing groundwater resources are required to prevent further deterioration of groundwater resources. Policies should be made and implemented to ensure “green” exploitation of geothermal water.     

Spatial distribution of trace elements associated with organic carbon along the Beiyun River basin,Beijing,China

Pollution resulting from terrestrial and aquatic trace elements has become a severe problem across the world. Organic carbon(OC) content has a high affinity for metallic contaminants and it acts as a significant sink for trace elements. The decomposition of OC content directly influences the bioavailability of trace elements. The decomposition of OC content and OC distribution vary spatially, these processes affect the release of trace elements and need further research. In the current study, se...     

Understanding the dynamics and contamination of an urban aquifer system using groundwater age (14C, 3H,CFCs) and chemistry

The quality of the groundwater supplying drinking water to the Guadalajara metropolitan area has deteriorated due to both endogenic and exogenic processes. Previous studies of this complex neotectonic volcanic environment suggest that the sources of contamination here are underground fluids derived from an active volcanic center and surface wastewater derived from regional land‐use intensification. This study uses isotopic, gaseous, and chemical signatures to more comprehensively characterize this groundwater flow and its contamination paths. Groundwater is mainly recharged at the La Primavera Caldera to the west and is discharged into the Santiago River to the east. The exception to this trend is the Toluquilla area, where groundwater most likely represents rainfall originating from outside the basin limits. Evaporation affects groundwater in these areas, especially waters that have been affected by recycling below urban areas in the Atejamac area and by intensive agricultural activity in the Toluquilla area. Additionally, we present evidence that groundwater flow through alluvial sediments and tuffs in deeper wells mixes with a lower aquifer unit in basaltic‐andesitic rocks, which are in contact with hydrothermal fluids. Groundwater ages range from postbomb in the western and northwestern regions of the study area (i.e., the Atemajac aquifer unit) to Late Pleistocene in the southern and southeastern regions (i.e., the Toluquilla aquifer unit). Recently recharged water records little mixing and is located mostly in or near the La Primavera volcanic system. As groundwater undergoes gravitational flow towards discharge areas, it mixes with older water components. Chloride and sodium concentrations above natural background levels are primarily related to volcanic activity, nitrate is associated with human activities, and sulfate originates from both anthropogenic sources and water–rock interactions. Nitrate originating from land‐use activities (such as sewers, septic tanks, landfills, and agricultural fields) that is introduced into the deeper part of the groundwater system is expected to travel with the groundwater to the discharge areas because oxidizing conditions will prevent microbial reduction. See Supplementary Information.     

Heavy metal contamination in coastal sediments and soils near the Brazilian Antarctic Station, King George Island

This paper investigates the natural and anthropogenic processes controlling sediment chemistry in Admiralty Bay, King George Island, Antarctica, emphasizing the area affected by the Brazilian Antarctic Station Comandante Ferraz (Ferraz). Total and bioavailable concentrations of sixteen elements were determined in 32 sediment and 14 soils samples. Factor analysis allowed us to distinguish three groups of samples: (1) Ferraz sediments, with higher content of total trace metals and organic matter; (2) control sediments, with intermediate characteristics; (3) Ferraz soils, with higher bioavailability of most metals due to its oxidizing condition and low organic matter content. Major elements such as Fe, Al, Ca and Ti presented similar levels in all three groups. Enrichment factor calculations showed that paints, sewage and petroleum contamination enhanced metal concentrations in Ferraz surface sediments as follows: B, Mo, and Pb (>90%); V and Zn (70-80%); Ni, Cu, Mg, and Mn (30-40%). Despite evidence of contamination in these sediments, the low bioavailability, probably caused by iron-sulfide, indicates small environmental risks.     

Evaluation of the potential risks of heavy metal contamination in rice paddy soils around an abandoned Hg mine area in Southwest China

To assess the potential ecological and health risks of trace elements(Hg,Cd,As,Mn,Sb,Pb,Cu,Ni,Cr,and Zn),a total of 138 soil samples from rice paddies were collected during the rice harvest season in the Wanshan mining area,Guizhou Province,Southwest China.Factors of the pollution load index(PLI),geo-accumulation index(I-Geo),enrichment factor(EF),and risk index(RI)were determined.High concentrations of Hg,Sb,As,Zn,Cd,Cu,and Mn were observed in the soils.The PLI,I-Geo,and EF results all showed high levels of contamination by Hg and Sb and moderate levels of contamination by As,Pb,Zn,Cu,Cd,and Mn.There was no significant contamination from Ni and Cr.The RI was very high,with Hg as the dominant pollutant,as expected,indicating that the historical large-scale Hg mining,as well as artisanal mining,has had a significant impact on the Wanshan area.Moreover,coal combustion,manganese factories,and the use of agrochemicals by the local population could also have an impact on the soil through the introduction of heavy metal loads.To address the current state of contamination,pollutant remediation and the regulation control of the anthropogenic activities in Wanshan are urgently needed.     

Trace element content of seagrasses in the Leschenault Estuary,Western Australia

Estuarine environments are particularly vulnerable to human impacts. In this study, trace elements in Ruppia megacarpa, Halophila ovalis, sediment and porewater were analysed to assess the potential contamination of the Leschenault Estuary, Western Australia, from a primarily agricultural drain. Sediment concentrations of Cd, Cu, Mn, and Ni and were highest nearest the drain while Al, As, Cr, Fe and Zn and were highest further from the drain. H. ovalis showed greater accumulation of Fe, Al, and As than R. megacarpa. Concentrations of Fe, Al, As, and Ni were generally higher in below-ground plant parts than above, suggesting uptake of these trace elements via the sediment-route pathway. This study suggested that the drain was a source of Cu and Mn, with these elements entering the estuary through water inflows. As and Fe, were highest furthest from the drain suggesting input of trace elements from sources other than the drain under study.     

Factors contributing to nitrate contamination in a groundwater recharge area of the North China Plain

Nitrate contamination is a common problem in groundwater of the North China Plain (NCP) owing to overuse of fertilizers and discharge of wastewater. Accordingly, it is important to investigate nitrate contamination in recharge areas to understand the fate of nitrate in the plains area. In this study, the spatial and temporal distribution characteristics of nitrate and factors contributing to its sources and transformation in shallow groundwater of the Beiyishui River watershed, NCP, were analysed by a combination of multiple regression and multi‐tracer methods. The nitrate concentration of 79% of the samples exceeded the natural environmental standard of 13.3 mg l^?1, while that of 23% of the samples exceeded the World Health Organization (WHO) drinking water standard of 50 mg l^?1. Groundwater age estimation of the hill regions based on chlorofluorocarbons (CFCs) revealed a mix of young water from 1982 to 1990 and old, low CFC water. The analysis based on the variations in land use in past years revealed that part of the grassland was converted into woodland between 1980 and 1995; therefore, the land use at the recharge time was used to determine which surface conditions influence groundwater nitrate concentrations. Multiple regression analysis showed that point source pollution contributed to the high concentration of nitrate in the hill region. Fertilizer application associated with land use change from grassland to woodland was also related to the present nitrate concentration. In the plains area, the contribution of fresh water from fault fractures and denitrification led to 31 to 72% and 6 to 51% reductions in nitrate concentrations, respectively. Our results suggested that controlling point source contamination and fertilizer input to hilly regions of the study will prevent groundwater of the plains area from deterioration in future years by mixing fresh water into the aquifers and decreasing denitrification, and therefore nitrate concentrations. Copyright © 2015 John Wiley & Sons, Ltd.     

Inverse methods for subsurface flow: A critical review of stochastic techniques

The development of stochastic methods for groundwater flow representation has undergone enormous expansion in recent years. The calibration of groundwater models, the inverse problem, has lately received comparable attention especially and almost exclusively from the stochastic perspective. In this review we trace the evolution of the methods to date with a specific view toward identifying the most important issues involved in the usefulness of the approaches. The methods are critiqued regarding practical usefulness, and future directions for requisite study are discussed.     

Pre‐drill Groundwater Geochemistry in the Karoo Basin,South Africa

Enhanced production of unconventional hydrocarbons in the United States has driven interest in natural gas development globally, but simultaneously raised concerns regarding water quantity and quality impacts associated with hydrocarbon extraction. We conducted a pre‐development assessment of groundwater geochemistry in the critically water‐restricted Karoo Basin, South Africa. Twenty‐two springs and groundwater samples were analyzed for major dissolved ions, trace elements, water stable isotopes, strontium and boron isotopes, hydrocarbons and helium composition. The data revealed three end‐members: a deep, saline groundwater with a sodium‐chloride composition, an old, deep freshwater with a sodium‐bicarbonate‐chloride composition and a shallow, calcium‐bicarbonate freshwater. In a few cases, we identified direct mixing of the deep saline water and shallow groundwater. Stable water isotopes indicate that the shallow groundwater was controlled by evaporation in arid conditions, while the saline waters were diluted by apparently fossil meteoric water originated under wetter climatic conditions. These geochemical and isotopic data, in combination with elevated helium levels, suggest that exogenous fluids are the source of the saline groundwater and originated from remnant seawater prior to dilution by old meteoric water combined with further modification by water‐rock interactions. Samples with elevated methane concentrations (>14 ccSTP/kg) were strongly associated with the sodium‐chloride water located near dolerite intrusions, which likely provide a preferential pathway for vertical migration of deeply sourced hydrocarbon‐rich saline waters to the surface. This pre‐drill evaluation indicates that the natural migration of methane‐ and salt‐rich waters provides a source of geogenic contamination to shallow aquifers prior to shale gas development in the Karoo Basin.     

Assessment of the historical trace metal contamination of sediments in the Elizabeth River, Virginia

Two sediment cores (Southern Branch, PC-1, and Western Branch, WB-2) were taken from the highly industrialized Elizabeth River, Virginia. The concentrations of trace metals cadmium, cobalt, chromium, copper, nickel, lead and zinc, major elements iron, manganese and aluminum, organic carbon content and the specific surface area of the sediments were determined in each of the cores. Down-core variations in metals varied significantly in each core with maximum contamination events occurring at different times in different portions of the river. In PC-1, maximum metal concentrations were seen after the appearance of (137)Cs. In contrast, the highest levels in WB-2 occurred well before the appearance of (137)Cs. Although stricter environmental regulations have caused a decrease in metal concentrations since the 1980s, the concentrations in the surface sediments of many trace metals were elevated to levels 2-5 times higher than the levels at the bottom of the cores in both the Southern and Western Branches of the river.     

Tracing contamination sources through phenotypic characterization of Escherichia coli isolates from surface water and groundwater in an agro-ecosystem

The objective of this research was to evaluate the groundwater chemical and bacteriological quality in the Barranquita-Knutzen basin (Córdoba, Argentina). The main purpose was to trace contamination through the examination of bacteriological parameters and antibiotic resistance of Escherichia coli, relating them to surface water, hydrogeological features and land use. Thus, 40 water samples were collected. The major chemical components and bacterial indicators were determined and antibiotic resistance was analysed using standard methods. Multivariate factorial analysis showed that the first principal component (PC) reveals the process of water mineralization, while the second and the third PCs explain a low percentage of variance, but collect chemical constituents and total and faecal coliform bacteria, respectively, revealing specific contamination situations. The observed antibiotic resistance profiles of E. coli and their relation with the land uses revealed that the source of faecal contamination in water is mainly from animal residues.     

Ecological risk assessment using trace elements from surface sediments of Izmit Bay (Northeastern Marmara Sea) Turkey

The aim of this study was to study ecological risk assessment of trace elements (As, Cd, Cr, Cu, Ni, Pb and Zn) in Izmit Bay surface sediments in the <63 microm fraction. Sediment samples were collected from 8 sites along the north coastline of the bay. Samples were subjected to a total digestion technique and analyzed for major (organic carbon) and minor (As, Cd, Cr, Cu, Ni, Pb and Zn) elements. Sediments heavily contaminated are evaluated by the Sediment Quality Guidelines (SQG) of US EPA. The degree of contamination (Cd) is estimated as very high at each site. Two sets of SQGs, effect range-low/effect range median values and TEL/probable effect level (PEL) values were used in our study. Sediments from the each site are judged toxic when two or more of the PEL values exceed EPA guidelines. Our results are in agreement with previously reported sediment toxicity test results.     

Characteristics of organic matter as indicators of pollution from small‐scale livestock and nitrate contamination of shallow groundwater in an agricultural area

The main purpose of this study was to examine the hydrogeochemical factors leading to nitrate contamination of shallow groundwater in an agricultural area. Another purpose was to identify relationships between variations in organic matter levels (as estimated by the BOD and COD parameters) of groundwater that transports effluent from small‐scale livestock holdings. Major cations, anions, BOD and COD of organic matter and total coliforms were analysed. It was found that groundwaters beneath cultivated areas and areas carrying livestock had higher concentrations of calcium, nitrate and chloride than did freshwater. Above all, the nitrification process increased concentrations of nitrate. Nitrate levels were depressed in some places where the groundwater was low in dissolved oxygen. Groundwaters affected by livestock activities showed high concentrations of organic matter (BOD, COD) and high microbial concentrations (as indicated by total coliforms). The COD/BOD ratio increased in the downward direction. It was inferred that this was due to the faster loss of easily biodegradable organic matter compared with non‐biodegradable organic matter proceeding away from a discharge. Accordingly, it is possible to trace effluent in a small area back to a point source by monitoring the COD/BOD ratio of groundwater. Copyright © 2003 John Wiley & Sons, Ltd.     

Applying the HPT‐GWS for Hydrostratigraphy,Water Quality and Aquifer Recharge Investigations

The primary objective of this study was to evaluate use of the hydraulic profiling tool‐groundwater sampler (HPT‐GWS) log data as an indicator of water quality (level of dissolved ionic species) in an alluvial aquifer. The HPT‐GWS probe is designed for direct push advancement into unconsolidated formations. The system provides both injection pressure logs and electrical conductivity (EC) logs, and groundwater may be sampled at multiple depths as the probe is advanced (profiling). The combination of these three capabilities in one probe has not previously been available. During field work it was observed that when HPT corrected pressure (P_c) indicates a consistent aquifer unit then bulk formation EC can be used as an indicator of water quality. A high correlation coefficient (R ² = 0.93) was observed between groundwater specific conductance and bulk formation EC in the sands and gravels of the alluvial aquifer studied. These results indicate that groundwater specific conductance is exerting a controlling influence on the bulk formation EC of the coarse‐grained unit at this site, and probably many similar sites, consistent with Archie's Law. This simple relationship enables the use of the EC and P_c logs, with targeted water samples and a minimum of core samples, to rapidly assess groundwater quality over extended areas at high vertical resolution. This method was used to identify both a brine impacted zone at the base of the aquifer investigated and a groundwater recharge lens developing below storm water holding ponds in the upper portion of the same aquifer. Sample results for trace level, naturally occurring elements (As, Ba, U) further demonstrate the use of this system to sample for low level groundwater contamination.     

The geology, petrology, and petrogenesis of Saba Island, Lesser Antilles

Saba is the northernmost volcano along the Lesser Antilles island-arc chain. The Lesser Antilles arc results from the west-northwest subduction of the Atlantic lithosphere beneath the Caribbean Plate. Sediment thickness along the trench decreases northward away from sediment sources on the continent of South America. We focused our attention on Saba precisely because it is the furthest away from documented geochemical effects in the southern arc volcanics of the large sediment thicknesses — normally attributed to both source or upper level contamination (i.e. assimilation).Field mapping, petrology, mineralogy, K–Ar dating, and geochemical analyses (major and trace element) indicate a complex history of magma petrogenesis including crystal fractionation, magma mixing, and, surprisingly, crustal assimilation. This is the first time assimilation has been documented in the northern section of the Lesser Antilles arc. Magma mixing shows up in the field as banded pumice and petrographically and mineralogically as complex zoning in phenocrysts (such as reverse zoning in plagioclase), disequilibrium mineral assemblages (e.g. quartz and olivine), and disequilibrium between minerals and whole-rock compositions (e.g. forsterite content of olivine). Mass-balance modeling of major and trace elements support our contention that crystal fractionation (including amphibole) played an important role in magma evolution. However, various geochemical trends can only be explained by assimilation-fractional crystallization based on the fact that the trends of various trace elements and trace-element ratios vary with increasing silica. Finally, we could find no evidence of sediment source contamination in the most mafic rocks. It may exist but is overprinted by the later assimilation effects.     

Dissolved metal contamination in the East River-Long Island sound system: potential biological effects

A suite of dissolved trace metals (Ag, Cd, Cu and Pb), inorganic nutrients (NO(3), PO(4)), and chlorophyll a was measured along a 55 mile transect from the East River into western and central Long Island Sound. The main objectives of this study were to determine the relative levels of contamination from sewage, and to assess its possible biological impact on local waters. The East River-Long Island Sound system receives large volumes of treated sewage and industrial effluent as a result of the heavy urbanization of the area. Despite these strong environmental pressures, this study is among the first to report dissolved metal levels from that region. Consistent with the locations of anthropogenic sources, a strong east-west concentration gradient was observed for Ag, Pb, NO(3) and PO(4) with the highest levels found in the East River. In contrast, dissolved Cd and Cu were relatively constant throughout the area of study, suggesting that sewage sources have a more limited influence on the levels of those metals. Remobilization from contaminated sediments may represent the primary source of Cd and Cu to the Long Island Sound under low-runoff conditions in summer. Chlorophyll a concentrations, used as an indicator of total biomass, were also low in the East River. These low chlorophyll concentrations could not be explained by nutrient or light limitation, water column stratification, or to advection of phytoplankton out of the river during tidal flushing. These preliminary results suggest a potential toxic effect of sewage on the biological communities of the East River.