High-resolution profiles of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment

The remobilization of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment cores at Yingkou was assessed using diffusive equilibrium in thin films and diffusive gradients in thin films techniques. A relatively anoxic system (+33.7 to ?224.1 mV) in the sediment cores might cause the reductive release of iron, manganese and cobalt into pore water from the estuarine sediment. High-average concentrations of iron (47.85 μg ml^?1) and manganese (3.81 μg ml^?1) were observed using diffusive equilibrium in thin films on the sediment core, but the concentration of cobalt (18.02 ng ml^?1) was relatively low. A strong correlation between iron and cobalt was observed based on the vertical profiles of the metals. Manganese and iron were more readily released from the solid phase to the solution. The peak cobalt, copper and zinc concentrations were observed in the upper layer (2–4 cm) measured using diffusive gradients in thin films. However, the peak iron, manganese and cobalt concentrations were located in the deeper layer (≥7 cm). In addition, the concentration profiles measured using diffusive gradients in thin films of cobalt, copper and zinc were independent of the iron, manganese and cobalt distribution with respect to depth.     

Assessment of groundwater water quality in central and southern Gulf Coast aquifer,TX using principal component analysis

Principal component analysis has been applied for source identification and to assess factors affecting concentration variations. In particular, this study utilizes principal component analysis (PCA) to understand groundwater geochemical characteristics in the central and southern portions of the Gulf Coast aquifer in Texas. PCA, along with exploratory data analysis and correlation analysis is applied to a spatially extensive multivariate dataset in an exploratory mode to conceptualize the geochemical evolution of groundwater. A general trend was observed in all formations of the target aquifers with over 75 % of the observed variance explained by the first four factors identified by the PCA. The first factor consisted of older water subjected to weathering reactions and was named the ionic strength index. The second factor, named the alkalinity index explained greater variance in the younger formations rather than in the older formations. The third group represented younger waters entering the aquifers from the land surface and was labeled the recharge index. The fourth group which varied between aquifers was either the hardness index or the acidity index depending on whether it represented the influences of carbonate minerals or parameters affecting the dissolution of fluoride minerals, respectively. The PCA approach was also extended to the well scale to determine and identify the geographic influences on geochemical evolution. It was found that wells located in outcrop areas and near rivers and streams had a larger influence on the factors suggesting the importance of surface water–groundwater interactions.     

Characterisation of the physicochemical qualities of a typical rural-based river: ecological and public health implications

The physicochemical qualities of a typical rural-based river were assessed over a 12-month period from August 2010 to July 2011 spanning the spring, summer, autumn and winter seasons. Water samples were collected from six sampling sites along Tyume River and analysed for total nitrogen, orthophosphate, biochemical oxygen demand (BOD), temperature, pH, dissolved oxygen (DO), electrical conductivity (EC), total dissolved solids (TDS) and turbidity. BOD regimes did not differ significantly between seasons and between sampling points and ranged from 0.78 to 2.76 mg/L across seasons and sampling points, while temperature ranged significantly (P < 0.05) between 6 and 28 °C. Turbidity varied significantly (P < 0.05) from 6 to 281 nephelometric turbidity units while TDS (range 24–209 ppm) and conductivity (range 47.6–408 mg/L) also varied significantly (P < 0.05) across sampling points with a remarkable similarity in their trends. Orthophosphate concentrations varied from 0.06 to 2.72 mg/L across seasons and sampling points. Negative correlations were noted between temperature and the nutrients, DO and temperature (r = ?0.56), and TDS and DO (r = ?0.33). Positive correlations were noted between TDS and temperature (r = 0.41), EC and temperature (r = 0.15), and DO and pH (r = 0.55). All nutrients were positively correlated to each other. Most measured parameters were within prescribed safety guidelines. However, the general trend was that water quality tended to deteriorate as the river flows through settlements, moreso in rainy seasons.     

Assessment of heavy metals in sediment and in suspended particles affected by multiple anthropogenic contributions in harbours

La Goulette, Rades and Sidi Bou Said harbours are considered as the most important commercial and tourist ports in the Gulf of Tunis. They are located on the northeast coast of Tunis and receive industrial and municipal wastewaters from Tunis city. The contamination level of copper, lead, zinc, cadmium, manganese, iron, total nitrogen and total organic carbon in the surface sediments was assessed on the basis of the enrichment index factors and corresponding to sediment quality guidelines. The results revealed moderate to highly elevated concentrations near to the sites of intense industrial, shipping and/or commercial activities suggesting a direct influence of these sources. In winter and summer, concentrations varied for cadmium, 0.28–1.40 mg kg^?1; lead, 18–217 mg kg^?1; zinc, 87–459 mg kg^?1; copper, 8–121 mg kg^?1; manganese, 208–254 mg kg^?1; and for iron, 24–40 g kg^?1. Furthermore, in summer the concentration of the total organic carbon and the total nitrogen contents range between 4.3–6.5 % and 0.06–0.49 % with an average value of 5.9 and 0.15 %, respectively. Whereas, in winter, total organic carbon and the total nitrogen concentrations varied between 2.3–9.6 % and 0.03–0.22 % with an average value of 6.1 and 0.14 %, respectively. The levels of lead, copper, zinc and iron in suspended particulate matter content range between 3.1–27.5 mg kg^?1; 0.4–11.7 mg kg^?1; 1–1.5 mg kg^?1; 1.2–1.7 g kg^?1, respectively. This study revealed that heavy metals pollution is mainly localized in the commercial (Rades) and fishing (La Goulette) harbours and not in the yachting (Sidi Bou Said) harbour.     

Identification and characterization of the encrusting materials in a coastal liquefied petroleum gas storage cavern

An examination was carried out of the encrusting materials on the seepage removal pumps in a bottom sump of an undersea liquefied petroleum gas (LPG) cavern. The studied cavern, constructed at 8 km off the western coast of Korea, facing the Yellow Sea, is at 130–150 m below the seabed. Since the first filling of the LPG into the cavern, it has suffered from the unexpected problem of a thick encrustation of unknown materials on the seepage removal pumps of the cavern. The XRD and XRF analyses revealed that the encrustation materials were mainly iron (hydro)oxides and carbonate mineral (aragonite). Based on the geological setting below the cavern site, it was inferred that iron oxides found in the Pleistocene sandy sediment and the Precambrian gneiss might be supplying ferrous iron to the cavern waters under an anaerobic condition, evidenced by low dissolved oxygen and negative redox potential in the cavern water. A significant change in the hydraulic condition near the pump intake and mixing the cavern water with oxic waters supplied through re-circulated seawater and terrestrial groundwater discharge, would precipitate the dissolved iron. Precipitation of the carbonate mineral is thought to have occurred due to over-saturation of calcium and bicarbonate, which may have resulted from the dissolution of cement grouting materials used during the undersea cavern construction and submarine groundwater discharge (SGD). This study reports the iron and carbonate precipitation in the man-made undersea cavern, which is affected by the surrounding hydrogeological condition and the SGD.     

Application of the chemometric approach to evaluate the spatial variation of water chemistry and the identification of the sources of pollution in Langat River, Malaysia

The current study presents the application of selected chemometric techniques—hierarchical cluster analysis (HCA) and principal component analysis (PCA)—to evaluate the spatial variation of the water chemistry and to classify the pollution sources in the Langat River. The HCA rendered the sampling stations into two clusters (group 1 and group 2) and identified the vulnerable stations that are under threat. Group1 (LY 1 to LY 14) is associated with seawater intrusion, while group 2 (LY 15 to LY 30) is associated with agricultural and industrial pollution. PCA analysis was applied to the water datasets for group 1 resulting in four components, which explained 85 % of the total variance while group 2 extracted six components, explaining 88 % of the variance. The components obtained from PCA indicated that seawater intrusion, agricultural and industrial pollution, and geological weathering were potential sources of pollution to the study area. This study demonstrated the usefulness of the chemometric techniques on the interpretation of large complex datasets for the effective management of water resources.     

Small Spatial Scale Variation in Fish Assemblage Structure in the Vicinity of the Northwestern Gulf of Mexico Hypoxic Zone

Seasonal hypoxia [dissolved oxygen (DO)?≤?2 mg?l^?1] occurs over large regions of the northwestern Gulf of Mexico continental shelf during the summer months (June–August) as a result of nutrient enrichment from the Mississippi–Atchafalaya River system. We characterized the community structure of mobile fishes and invertebrates (i.e., nekton) in and around the hypoxic zone using 3 years of bottom trawl and hydrographic data. Species richness and total abundance were lowest in anoxic waters (DO?≤?1 mg?l^?1) and increased at intermediate DO levels (2–4 mg?l^?1). Species were primarily structured as a benthic assemblage dominated by Atlantic croaker (Micropogonias undulatus) and sand and silver seatrout (Cynoscion spp.), and a pelagic assemblage dominated by Atlantic bumper (Chloroscombrus chrysurus). Of the environmental variables examined, bottom DO and distance to the edge of the hypoxic zone were most strongly correlated with assemblage structure, while temperature and depth were important in some years. Hypoxia altered the spatial distribution of both assemblages, but these effects were more severe for the benthic assemblage than for the pelagic assemblage. Brown shrimp, the primary target of the commercial shrimp trawl fishery during the summer, occurred in both assemblages, but was more abundant within the benthic assemblage. Given the similarity of the demersal nekton community described here to that taken as bycatch in the shrimp fishery, our results suggest that hypoxia-induced changes in spatial dynamics have the potential to influence harvest and bycatch interactions in and around the Gulf hypoxic zone.     

Holocene estuarine sediments as a source of arsenic in Pleistocene groundwater in suburbs of Hanoi,Vietnam

Groundwater pollution by arsenic is a major health threat in suburban areas of Hanoi, Vietnam. The present study evaluates the effect of the sedimentary environments of the Pleistocene and Holocene deposits, and the recharge systems, on the groundwater arsenic pollution in Hanoi suburbs distant from the Red River. At two study sites (Linh Dam and Tai Mo communes), undisturbed soil cores identified a Pleistocene confined aquifer (PCA) and Holocene unconfined aquifer (HUA) as major aquifers, and Holocene estuarine and deltaic sediments as an aquitard layer between the two aquifers. The Holocene estuarine sediments (approximately 25–40 m depth, 9.6–4.8 cal ka BP) contained notably high concentrations of arsenic and organic matter, both likely to have been accumulated by mangroves during the Holocene sea-level highstand. The pore waters in these particular sediments exhibited elevated levels of arsenic and dissolved organic carbon. Arsenic in groundwater was higher in the PCA (25–94 μg/L) than in the HUA (5.2–42 μg/L), in both the monitoring wells and neighboring household tubewells. Elevated arsenic concentration in the PCA groundwater was likely due to vertical infiltration through the arsenic-rich and organic-matter-rich overlying Holocene estuarine sediments, caused by massive groundwater abstraction from the PCA. Countermeasures to prevent arsenic pollution of the PCA groundwater may include seeking alternative water resources, reducing water consumption, and/or appropriate choice of aquifers for groundwater supply.     

Application of geospatial modelling technique in delineation of fluoride contamination zones within Dwarka Basin,Birbhum, India

Dwarka River Basin is one of the fluoride affected river basin in Birbhum, West Bengal. In the present research work, various controlling factors for fluoride contamination in groundwater i.e., geology, aquifer type, groundwater table, soil, rainfall, geomorphology, drainage density, land use land cover, lineament and fault density, slope and elevation were considered to delineate the potential fluoride contamination zones within Dwarka River Basin in Birbhum. Assigning weights and ranks to various inputs factor class and their sub-class respectively was carried out on the basis of knowledge driven method. Weighted overlay analysis was carried out to generate the final potential fluoride contamination zones which are classified into two broad classes i.e., ‘high’ and ‘low’, and it is observed that major portion of the study area falls under low fluoride contamination category encompassing 88.61% of the total area which accounts for 759.48 km² and high fluoride contaminated region accounts for 11.40% of the total study area encompassing an area of about 97.67 km². Majority of high fluoride areas fall along the flood plain of Dwarka River Basin. Finally, for validation 197 reported points within Dwarka having fluoride in underground water are overlaid and an overall accuracy of 92.15% is observed. An accuracy of 83.21% and 84.24% is obtained for success and prediction rate curve respectively.     

Identifying key hydrochemical processes in a confined aquifer of an arid basin using multivariate statistical analysis and inverse modeling

Tertiary fractured permeable confined aquifer, which covered about 70 % of the studying area, played an important role in alleviating drinking water shortages. However, about 58 and 79 % of the groundwater samples exceeded the desirable limits for fluoride (1.5 mg/L) and TDS (1,000 mg/L). Two multivariate statistical methods, hierarchical cluster analysis (HCA) and principal components analysis (PCA), were applied to a subgroup of the dataset in terms of their usefulness for groundwater classification, as well as to identify the key processes controlling groundwater geochemistry. In the PCA, two principal factors have been extracted, which could explain 73 % of the total data variability. Among them, factor 1 revealed the source of groundwater salinity and factor 2 explained the elevated fluoride. Two major groups were classified by HCA and Group 1 was near the groundwater recharge zone and Group 2 was mainly distributed over the groundwater discharge zone. Inverse modeling (NETPATH) results indicated that the hydrochemical evolution was primarily controlled by (1) the dissolution of mirabilite, gypsum and halite for the source of groundwater salinity; (2) the release of the adsorbed fluoride through desorption or through competition with HCO₃ ^? under alkalinity condition for the elevated fluoride in the groundwater.     

Development of tools to estimate conveyance losses in the Truckee River, USA

A method to estimate stream conveyance losses, including stream bank seepage and evapotranspiration from riparian areas, was developed for the Truckee River in California and Nevada (USA). Aquifer diffusivity is the primary variable required to compute aquifer head and seepage. Head and seepage conceptual models developed in previous studies were calibrated using stream stage and aquifer head at five sites along the Truckee River. The equations for head require numerical convolution to solve. It was found that head is insensitive to diffusivity and a single value for diffusivity provides good results at all study sites. Also, because releases from storage are usually prescribed as a step increase in flow for a given period of time followed by a step decrease in flow, an analytic solution for volume of seepage can be used in place of numerical convolution. Under typical operating conditions, seepage volume represents a small fraction of the total reservoir releases. Uncertainty in seepage estimates can be reduced with increased accuracy in hydraulic conductivity. This work demonstrates a valuable technique to estimate conveyance losses under natural and managed stream flow.     

In situ and laboratory treatment tests for lowering of excess manganese and iron in drinking water sourced from river–groundwater interaction

Manganese and iron are essential nutrients at low doses. However, long-term exposure in high doses may be harmful. Human activities and natural sources are responsible for manganese and iron contamination in water. This study aimed to investigate the source of high manganese and iron contents in shallow groundwater, where the groundwater is used for drinking purpose, and to decrease the excess manganese and iron from shallow groundwater. Based on the on-site analytical results taken from the wells in the study area, iron contents in water samples varied between 30 and 200 μg/L, which were under the allowable limits of Turkish Drinking Water Standards (TDWS) (Water intended for human consumption, http://rega.basbakanlik.gov.tr/eskiler/2005/02/20050217-3.htm, 2005). However, manganese levels varied from 30 to 248 μg/L, which some of them are higher than the allowable limits of TDWS (Water intended for human consumption, http://rega.basbakanlik.gov.tr/eskiler/2005/02/20050217-3.htm, 2005) (50 μg/L), and EPA (http://water.epa.gov/drink/contaminants/index.cfm, 2006) (50 μg/L). The source of excess manganese is originated mainly from geogenic source besides Porsuk River interaction in shallow aquifer in the specific section of the study area. To decrease high manganese content from the well water and reservoir water, laboratory and in situ treatment tests were applied. Among these tests, chlorination, associated with filtration (by fine sand, active carbon and zeolite) and the use of different filtration procedures by cation exchange resin were determined as the most effective methods, which was not previously applied on-site as a combinative approaches to reduce the excess manganese in water.     

Secondary dispersion patterns of fluoride in the osor area,Province of Gerona,Spain

The distribution of fluoride in spring and stream waters, stream sediments and soils of the Osor district, Province of Gerona, northeastern Spain, has been studied. Fluoride was determined by use of a fluoride-sensitive electrode. This potentiometric method has been found useful for geochemical exploration for fluorite because of its simplicity and high sensitivity.Investigations of the fluoride contents of natural waters and stream sediments resulted in the discovery of new fluorite mineralizations.Secondary dispersion patterns of soils have been studied. Different analytical procedures to extract the fluoride have been used. The application of the methods in geochemical exploration surveys is discussed.     

Characteristics of groundwater in karstic region in northeastern Vietnam

The groundwater in the karst region of northeastern Vietnam is found in various structural zones such as the Ha Lang, Song Hien, Hon Gai, Song Lo, Song Gam, and Hoang Lien Son Zones, etc. Results from this study show that groundwater in this region is at different depths: ~120 m deep at Quang Ninh, ~100 m at Lang Son, ~80 m at Cao Bang (The most water-abundant depth observed at Cao Bang varies from 40 to 45 m) while it varies from 18–25 to 80 m deep at Quan Ba (Ha Giang), especially at Meo Vac (Ha Giang), where groundwater is observed at 700–800 m deep (equivalent to local base level of the Nho Que River). Overall, groundwater in the region is fresh with total minerals varying from 250 to 400 mg/l; except for the coastal area of Quang Ninh, where groundwater is characterized by much higher total minerals (M = 3–18 g/l) due to the mixing with the saline sea water. The chemistry of water in the region demonstrates that the water is mainly bicarbonate with a [HCO₃ ^?] concentration varying from 150 to 265 mg/l, pH is of 6.5–8.1, and its hardness is of 3.7–6.0 meq/l.     

Stable isotopic information for hydrological investigation in Hailuogou watershed on the eastern slope of Mount Gongga, China

Hydrological systems have been seriously affected by changes of glaciations and snow covers in Mount Gongga, Sichuan, China, but the relevance of ice-snow melt for alpine river basin hydrology is so far not well known. To better understand hydrological features of the Hailuogou River, changes of δ¹⁸O and δ²H were investigated by analyzing 117 water samples collected from May 2008 to November 2009. Our results show that the stream water contains a relatively intermediate magnitude of isotopic variations, with δ¹⁸O ranging from ?18.09 to ?13.08 ‰ and δ²H from ?126.5 to ?88.8 ‰. The average values are both higher than those of ice-snow meltwater, but lower than those of meteoric water. These data also show a gradually increasing trend from upstream to downstream, and these changes might document the fingerprint of ice-snow melt in the headwater region and indicate the increasing recharge of heavy isotope-enriched waters with flow distance. The similarity in slopes of δ²H and δ¹⁸O relationship for meteoric waters and stream waters suggests that the isotopic signature of precipitation is well preserved in stream flow, and during the rainfall and stream flow the evaporation is only minor. Based on δ¹⁸O model, the results suggested that the fraction of ice-snow meltwater input over the total stream flow ranged from 84.50 to 86.52 % in the headwater region, but the fraction of ice-snow meltwater input from upper basin downward was significantly decreased. The study demonstrates that ice-snow meltwater is a substantially important water source in alpine regions on the edge of Tibetan Plateau.     

Chemometric approach integrated with capillary electrophoresis for the investigation of public water system sources and quality

A chemometric approach coupled with capillary electrophoresis based on the hierarchical cluster analysis and principal component analysis has been applied for the investigation of the water quality in the Golcuk-Isparta region (Lake District of Turkey). In the research area, Egirdir Lake, Golcuk Lake and surrounding ground and domestic waters have been utilized as drinking water resources. Golcuk Lake is distinctive in terms of high fluoride content (3.50 ± 0.21 mg/mL) which is endemic in volcanic areas where the water flow through volcanic rocks and sediments. Based on the analysis of major anions chloride, sulfate, nitrate and fluoride with capillary electrophoresis, twenty-four drinking water sampling sites in the research area were classified into four classes using the hierarchical cluster and principal component analysis. Combining the research area investigation results of hierarchical cluster and principal component analysis, it was found that fluoride concentration is the major diagnostic variable to determine the quality of drinking waters, and all the other anions are the important classification factors to predict the resources of the drinking water samples, individually. To sum up, this study reveals the potential of the use of capillary electrophoresis in combination with chemometric techniques for the determination of the quality and origin of drinking waters.     

Organic matter scavenging of copper, zinc, molybdenum, iron and manganese, estimated by a sodium hypochlorite extraction (pH 9.5)

The importance of trace metal scavenging by organic matter in geochemical samples was estimated using an alkaline sodium hypochlorite extraction to leach copper, zinc, molybdenum, iron and manganese from a variety of soils, and stream and lake sediments collected on the Nechako plateau, central British Columbia. The reagent oxidizes or dissolves most forms of organic matter, together with any sulphide minerals, to give strongly coloured extracts containing the associated trace elements at a pH where solution of other sample fractions is at a minimum. Metals precipitated due to alkaline conditions are redissolved by a succeeding distilled-water leach (pH 3.0 ± 0.3).A large fraction of the copper, zinc, molybdenum, and manganese held within the organic fraction of the A soil horizon is liberated whereas only minor amounts of copper, zinc, and manganese are released from inorganic soil (B and C) horizons. Molybdenum, however, is relatively soluble in all soils as the molybdate ion. Despite similar concentrations of organic matter in A horizon soils and stream sediments the latter release a lower proportion of their trace element content. Behaviour of the organic fraction of lake sediments varies from lake to lake and there is great variability in the association of copper, zinc, molybdenum and manganese with organic matter even within the same lake.The presence of organic matter in samples subjected to other partial extractions can be a deleterious factor if the organic fraction is not first removed by a hypochlorite extraction.     

Satellite altimetry for measuring river stages in remote regions

The advent in satellite altimetry with the most accurate satellite radar altimeter since 1992 and its successive missions have enabled the routine global monitoring of water-level (or stage) for surface waters and changes in the quantities of dammed water reservoirs. However, satellite altimeter measurements typically have spatial resolution capable of observing only large water bodies, such as major lakes and rivers. This paper addresses the challenges of how to investigate water levels in medium (~?1 km in width) to small (~?100 m and narrower) rivers. Comparisons between the ENVISAT altimetry ICE-1 waveform retracking height and standard water-level measurements for multiple sections of Ohio River, Columbia River, and Red River of the North in the United States (US) reveals that the satellite altimetry measured water levels agree well with those observed at nearby US Geological Survey gaging stations over the 10-year period starting from 2002. The significant results include those obtained at Thompson, North Dakota (ND, correlation coefficient or R value of 0.76 between satellite and in situ water-level measurements) and Fargo, ND (R?=?0.74), where the stream channels of Red River are merely?~?50 m and ~?40 m wide, respectively, under normal climatic conditions. In addition, demonstrations of the approach over largely inaccessible portions of Tigris–Euphrates Rivers and Helmand River in the Middle East aided in understanding hydrology in these systems. This study demonstrates the ability of satellite radar altimetry to characterize rivers in these study regions which are much narrower than 100 m in width.     

Identification of sources of chemical constituents in groundwater from the Vilnius wellfields, Lithuania

The only source of drinking water in Vilnius City, Lithuania's capital, is groundwater. It can be supplied from 20 wellfields situated in the City or its environs. About half of them (11) are located in the valley of the Neris River crossing the City. The exploited aquifers were formed by melting continental glaciers and modified by the river. Until 1990 groundwater resources had not been conserved—the per capita consumption for domestic use in Vilnius reached 350 l/day. After 1990, due to the increasing cost of supplying drinking water, its consumption was reduced by a factor of three. As pumping rates of wellfields in Vilnius were increased or decreased, the groundwater quality was changed significantly. It is mainly affected by the surface water and shallow aquifers of the hydrologic system. The unoxidised organic matter that enters the exploitable aquifers from rivers and polluted shallow groundwater consumes scarce oxygen resources, thus creating anoxic conditions favourable for increasing the accumulation of iron, manganese and ammonium. Modelling and monitoring data show that the concentrations of sulphates and chlorides in Vilnius wellfields indicate not only the rise of brackish water from below, but also downward seepage of polluted surface water into the aquifers.