Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection

Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.     

Distribution of iron and manganese in the Seine river estuary: approach with experimental laboratory mixing

The physico-chemical behaviour of iron and manganese has been observed during many surveys covering various hydrodynamic conditions in the Seine river estuary system. The results obtained confirm the non-conservative behaviour of these two metals. Generally, dissolved iron exhibits non-conservative removal and shows a rapid decrease in low salinity; it is moved from fresh waters with high concentrations to saline waters with very low concentrations. This can be attributed to the flocculation processes as confirmed by laboratory experiments. Dissolved manganese versus salinity curves exhibit a peak concentration in the low salinity zone. Laboratory mixing experiments have been undertaken comparing iron and manganese adsorption/desorption from suspended material versus salinity, using a series of water samples collected in the up-river and marine regions in order to assess the importance of particulate material and salinity on iron and manganese distributions. The salinity was controlled by varying the marine to fresh water ratio. The reaction kinetics aspect is developed in more detail for manganese in the last series of remobilization experiments starting from a stock of suspended particles collected in the upstream river site (Caudebec) in mixtures of waters, according to time and salinity. This study has allowed us to show that iron and manganese behaviour in the Seine estuary is strongly influenced: (i) by the high turbidity zone and by the presence of calcium carbonate which could stabilise the Mn(II) form; and (ii) by the increase of salinity, calcium, magnesium and suspended matter concentrations and by complex formation.     

Aluminium speciation in effluents and receiving waters

The respective speciation of aluminium in sewage effluent and in river water receiving effluent, has been examined. Results showed that concentrations of reactive aluminium changed over a timescale of hours and were controlled predominantly by pH. A minimum concentration of reactive aluminium occurred at a pH of approximately 6.8, coinciding with the prevalence of non-reactive, insoluble Al(OH)3 species. For receiving waters of low pH value, typically < pH 5, a large proportion of the 'naturally present' aluminium can be present in a reactive form at concentrations higher than the proposed Environmental Quality Standard (EQS). Mixing of waters of this type with effluent of a higher pH value leads to the precipitation of aluminium hydroxide. Mixing of effluent of pH value in the range 7.5-8.0 with river water in the same (or slightly higher) pH range appears to result in no appreciable change in the proportion of reactive aluminium; the change in concentration tends to be related simply to dilution. On the basis of a theoretical knowledge of aluminium speciation, results obtained in this work indicate that it is possible to make predictions about the proportion of reactive aluminium present in a receiving water, based on the pH values of the effluent water mixture and the concentration in the effluent. Reasonable comparisons between measured and predicted values were obtained at higher pH values, but the relationship was less certain at pH values less than 6.5 for which levels of reactive metal tended to be higher than the quality standard value.     

Chromium fractionation and speciation in natural waters

It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 μg L(-1). Cr(vi) was always below of the DL (0.3 μg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.     

Effect of ultrasonic agitation on the release of copper, iron, manganese and zinc from soil and sediment using the BCR three-stage sequential extraction

An ultrasonic bath and an ultrasonic probe have been used to develop rapid versions of the three-stage Community Bureau of Reference (BCR, now the Standards, Measurement and Testing Programme) sequential extraction procedure. The effect of the ultrasonic treatments on the extraction of copper, iron, manganese and zinc from a sewage sludge-amended soil has been assessed. Recoveries similar to those of conventional shaking (i.e., conventional value, +/- 30%) could generally be obtained for copper, manganese and zinc, but not for the important matrix element iron. With the use of compromise sonication conditions, steps 1, 2 and 3 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3, which was not performed with sonication) could be completed in 3, 5 and 1 min, respectively, using the ultrasonic probe, and in 3, 1 and 1 h, respectively, using the bath. The extraction procedures developed using the soil performed well when applied to lake sediment BCR CRM 601. Analyte partitioning was generally similar to that obtained with mechanical shaking, and overall metal recoveries were 84-98% of those obtained with the conventional BCR protocol, except for copper extracted with the probe (74%). Poorer performance (analyte recoveries, 58-104%) was obtained when the methods were applied to an intertidal sediment. This highlights the difficulty of developing a version of the BCR extraction, with ultrasonic assistance, which gives a performance equivalent to conventional shaking when applied to different substrates.     

Distribution, speciation, and risk assessment of selected metals in the gold and iron mine soils of the catchment area of Miyun Reservoir, Beijing, China

In order to investigate the metal distribution, speciation, correlation and origin, risk assessment, 86 surface soil samples from the catchment area around the Miyun Reservoir, Beijing, including samples from gold and iron mine areas, were monitored for fractions of heavy metal and total contents. Most of the metal concentrations in the gold and iron mine soil samples exceeded the metal background levels in Beijing. The contents of most elements in the gold mine tailings were noticeably higher than those in the iron mine tailings. Geochemical speciation data of the metals showed that the residual fraction dominated most of the heavy metals in both mines. In both mine areas, Mn had the greatest the acid-soluble fraction (F1) per portion. The high secondary-phase fraction portion of Cd in gold mine samples indicated that there was a direct potential hazard to organisms in the tested areas. Multivariate analysis coupled with the contents of selected metals, showed that Hg, Pb, Cr, and Ni in gold mine areas represented anthropogenic sources; Cd, Pb, and Cr in iron mine areas represented industrial sources. There was moderate to high contamination of a few metals in the gold and iron soil samples, the contamination levels were relatively higher in gold mine than in iron mine soils.     

Chemical speciation in natural and brine sea waters

A combined approach consisting of monitoring and thermodynamic modeling was used in order to calculate the concentration of trace element species in water samples of a broad salinity range and to explain their chemical behaviour. The study was performed on water samples (fresh, marine, hyper-saline) taken from the area of Burgas Bay, Bulgaria. The ion association model based on Debye-Hückel theory using the sst2008.dat database and the ion interaction model based on Pitzer theory using a new pit2010.dat database were compared and combined for the purposes of this study. The new pit2010.dat database combines the sst2008.dat database and the pitzer.dat database of the PHREEQCI computer program as well as the thermodynamic data for the elements Fe, Mn, Cu, Zn, Cd and Pb and their Pitzer ion interaction parameters. The results showed that: (1) the predominant species in fresh waters were free ions of Mn(2+) (73.6%), Zn(2+) (58.0%) and Cd(2+) ions (78.3%) as well as carbonate species CuCO?? (81.8%), PbCO?? (77.2%) and hydroxy species Fe(OH) ??(55.2%) and Fe(OH)+?(35.6%); (2) an increase in chloride species MeCl2(n)-(n)(n = 1-4, Me = Mn, Zn, Cu, Pb and Cd) and of the hydroxy species Fe(OH)?? for Fe was calculated for sea and hyper-saline water.     

Distribution and partitioning of iron, zinc, and arsenic in surface sediments in the Grande River mouth to Cuitzeo Lake, Mexico

Cuitzeo Lake is one of the largest and most important lakes in Mexico. It receives different types of pollutants through its main tributary, the Grande River of Morelia. The aim of this work was to determine if high concentrations of iron, zinc, and arsenic are present in sediments in an area near the river mouth to the lake, as well as to estimate the partitioning of these metals using a sequential extraction procedure in order to obtain information of their potential bioavailability. Sediment samples were collected from three different sites in Cuitzeo Lake and two sites in Grande River in both dry and wet seasons. A sequential extraction procedure was carried out to determine the concentrations of these elements in different geochemical phases of the sediments. Total metal concentrations were evaluated by using the enrichment factor and the geoaccumulation index. A comparison with sediment quality guidelines and shale values has also been made. The results indicate that sediments are considered unpolluted by iron and moderately polluted by zinc and arsenic. However, fractionation studies showed that significant amounts of Zn and As could be released to the lake ecosystem depending on the environmental conditions, representing a medium risk potential of bioavailability to the biota.     

Speciation and toxicological relevance of manganese in humans

Although manganese is an essential trace element, concerns are rising about the Mn exposure of humans being related to neurotoxic effects. This review summarizes several aspects of this topic to provide updated information on Mn related investigations, including chemical speciation of Mn-compounds. The paper starts with some chemical aspects of Mn and its compounds, enlightening oxidation states in general and in biological matrices. This is followed by considerations on natural sources of human exposure, on occupational sources and on anthropogenically caused environmental sources, for example from the use of methylcyclopentadienyl manganese tricarbonyl (MMT). Next, the paper deals with Mn levels in the human organism, showing normal Mn concentrations in various tissues or body fluids, and continues with the toxicology of Mn, i.e. absorption, distribution and excretion. Of specific concern is the transfer of Mn to the brain which is the relevant neurotoxic target. In this context, parallels and differences between primary and Mn-dependent Parkinsonism are discussed, concluding with a risk assessment and a consideration of susceptible groups. The main part of this review focuses on recent investigations on Mn speciation. Analytical problems and their solutions are also described for correct identification of relevant Mn-compounds in matrices of human origin. Finally, future needs are discussed, such as further investigations on those Mn-species which may overcome neural barrier control, on disease-modulated barrier control, on susceptibility to certain Mn-species, and on the interaction of Mn with Fe-homeostasis in the brain.     

Trace metal speciation and contamination in an intertidal estuary

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Tees estuary was carried out using a sequential extraction technique and Differential Stripping Voltammetry. The sediments of the estuary are mainly organic rich clay silts and metal concentrations exceed those in the water column. Speciation results show that contamination of the estuary is mainly from anthropogenic sources. Pb and Zn are associated with the reducible, residual and oxidisable fractions. The speciation pattern of Cd was similar to those of lead and zinc. However there were also some exchangeable and bound to carbonate fractions although these were less significant. Cu is largely associated with the oxidisable and residual fractions, with insignificant bound to carbonate, exchangeable and reducible fractions. The most bioavailable forms of the metals are the free inorganic ions. Total metal concentrations in the estuary display a downward trend since the 1970s.     

Contaminants in American alligator eggs from Lake Apopka,Lake Griffin,and Lake Okeechobee,Florida

Residues of organochlorine pesticides, polychlorinated biphenyls (PCBs), and 16 elements were measured in American alligator (Alligator mississippiensis) eggs collected in 1984 from Lakes Apopka, Griffin, and Okeechobee in central and south Florida. Organochlorine pesticides were highest in eggs from Lake Apopka. None of the elements appeared to be present at harmful concentrations in eggs from any of the lakes. A larger sample of eggs was collected in 1985, but only from Lakes Griffin, a lake where eggs were relatively clean, and Apopka, where eggs were most contaminated. In 1985, hatching success of artificially incubated eggs was lower for Lake Apopka, and several organochlorine pesticides were higher than in eggs from Lake Griffin. However, within Lake Apopka, higher levels of pesticides in chemically analyzed eggs were not associated with reduced hatching success of the remaining eggs in the clutch. Therefore, it did not appear that any of the pesticides we measured were responsible for the reduced hatching success of Lake Apopka eggs.     

Arsenic speciation in freshwater snails and its life cycle variation

Terrestrial snails are consumed by humans occasionally and they are an important food source for many creatures including fish and birds. Little is known about arsenic speciation in these gastropods, let alone life cycle variations. Here we report on the arsenic speciation in freshwater snails from Pender Island and Vancouver Island, B.C., Canada, which was determined on methanol/water extracts (43-59% extraction efficiency) by using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and HPLC-electrospray tandem mass spectrometry. The tetramethylarsonium ion, oxo-arsenosugars and thio-arsenosugars are the main arsenic species encountered. Arsenobetaine, which is commonly found in the marine environment, is minor. Live bearing snails Viviparidae sp. from Pender Island were maintained in aquaria and the arsenic speciation in the unborn, newly born, and adult animals was monitored. Oxo-arsenosugars predominate in the adults, whereas thio-arsenosugars seem to predominate in juveniles, suggesting that these arsenicals are snail metabolites.     

Stability and storage problems in organotin speciation in environmental samples

The stability of both tributyltin (TBT) and triphenyltin (TPT) in water, sediment, oysters and cockles was studied over a period of 18 months using several storage conditions. Butyltins were stable in unacidified sea-water stored in polycarbonate bottles in the dark at 4 degrees C for 7 months, but half of the TBT concentration was lost after 540 d. A comparable preservation time was achieved for butyltins stored on C18 cartridges at room temperature. However, phenyltins extracted from sea-water were stable for only 60 d stored on cartridges and even more pronounced losses (about 90% after 540 d) occurred when they were stored in either polycarbonate or Pyrex glass bottles. Losses of organotins were observed in sediments after air drying and pasteurization treatments using a freeze-dried sediment as a comparator, whereas both butyltin and phenyltin species remained stable in sediments stored at -20 degrees C for the 18 months tested, irrespective of the treatment used for stabilization. Air drying followed by pasteurization was shown to be superior to other treatments for the stabilization of organotin compounds in sediments stored at higher temperatures, but 30% of TBT was lost after 540 d at 25 degrees C. Finally, butyltins were stable in both frozen cockles and oysters in the dark over a 7 month period and in freeze-dried samples stored at 4 degrees C for 5 months, but TBT losses of about 70% were observed after 540 d.     

Levels and speciation of heavy metals in soils of industrial Southern Nigeria

A knowledge of the total content of trace metals is not enoughto fully assess the environmental impact of polluted soils. Forthis reason, the determination of metal species in solution isimportant to evaluate their behaviour in the environment andtheir mobilization capacity. Sequential extraction procedure wasused to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) fromfour contaminated soils of Southern Nigeria into sixoperationally defined geochemical species: water soluble,enchangeable, carbonates, Fe-Mn oxide, organic and residual.Metal recoveries were within ± 10% of the independentlydetermined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractionswas found in the exchangeable fraction, while Cu and Zn weresignificantly associated with the organic fraction. Thecarbonate fraction contained on average 14, 18.6, 12.6, 13 and11% and the residual fraction contained on average 47, 18, 33,50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming thatmobility and bioavailability of these metals are related to thesolubility of the geochemical form of the metals, and that theydecrease in the order of extraction sequence, the apparentmobility and potential bioavailability for these five metals inthe soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes ofcopper and nickel correlated positively and significantly withthe total content of metals, while mobility indexes of cadmiumand zinc correlated negatively and significantly with the totalcontent of metals.     

Phosphorous speciation in surface sediments of the Cochin estuary

Sequential chemical extraction using chelating agents were used to study the P dynamics and its bioavailability along the surface sediments of the Cochin estuary (southwest coast of India). Sediments were analyzed for major P species (iron bound P, calcium bound P, acid soluble organic P, alkali soluble organic P and residual organic P), Fe, Ca, total carbon, organic carbon, total nitrogen and total sulfur contents. An abrupt increase in the concentration of dissolved inorganic P with increasing salinity was observed in the study region. Iron-bound P exhibited a distinct seasonal pattern with maximum values in the monsoon season when fresh water condition was prevailed in the estuary. As salinity increased, the percentage of iron-bound P decreased, while that of calcium-bound P and total sedimentary sulfur increased. C/P and N/P ratios were low which indicate that large amounts of organic matter enriched with P tend to accumulate in surface sediments. The high organic P contribution in the sedimentary P pool may indicate high organic matter load with incomplete mineralization, as well as comparatively greater percentage of humic substance and resistant organic compounds. Principal component analysis is employed to find the possible processes influencing the speciation of P in the study region and indicate the following processes: (1) the spatial and seasonal variations of calcium bound P and acid soluble organic P was mainly controlled by sediment texture and organic carbon content, (2) sediment redox conditions control the distribution of iron bound P and (3) the terrigenous input of organic P is a significant processes controlling total P content in surface sediments. The bioavailable P was very high in the surface sediments which on an average accounts for 59 % in the pre-monsoon, 65 % in the monsoon and 53 % in the post-monsoon seasons. The surface sediments act as a potential internal source of P in the Cochin estuary.     

Arsenic contamination and speciation in surrounding waters of three old cinnabar mines

The impact of arsenic pollution in waters from the surroundings of three abandoned Hg mines in Northern Spain, as well as reaching the Caudal River, was evaluated. For assessing the factors controlling arsenic release, an extensive study based on the physicochemical characterization and multivariate statistical analysis of waters upstream and downstream each mine site was performed. Waters downstream of the La Soterra?a mine present the highest arsenic concentrations, up to 38.8 mg L(-1), coming mainly from the solubilisation of calcium, magnesium and strontium arsenates at a pH close to neutral. Although arsenic concentrations downstream of La Pe?a are markedly lower, these values remain too high, indicating that the encapsulation carried out in this spoil heap is insufficient. In addition, the high water flow in this point involves an extremely high input of arsenic to the surroundings (0.3 g s(-1)). Waters close to tailings from Los Rueldos suffer from acid mine drainage, provoking an important solubilisation of arsenic and heavy metals, a situation which is rapidly softened with distance. The study of arsenic speciation reveals the omnipresence of As(v) in waters from the three mines, whereas in La Pe?a low amounts of As(iii) were also detected. Different preservation methods for As speciation were compared, such as the addition of HCl, EDTA and the storage of samples without any additive, and no alteration of samples in any case up to nine months after the collection was observed. A study of seasonal variations of As and the main parameters affecting its concentration and speciation was completed throughout a year, showing no remarkable dependency with rainfall for any studied variable.     

湖泊富营养化控制理论与技术

从外部控制及内部控制二方面综述了湖泊富营养化的控制理论与技术,讨论了各项技术的优缺点及可行性,并提出了相应的发展方向。     

Chromium speciation in a contaminated groundwater: redox processes and temporal variability

Chromium species (Cr(III), Cr(VI), and Cr(III)-organic) in groundwater of a tannery contaminated area were monitored during pre- and post-monsoon seasons for a period of 3 years (May 2004 to January 2007). The objectives of the study were (1) to investigate the temporal variation of chromium species and other matrix constituents and (2) to study the redox processes associated with the temporal variation of chromium species. Samples were collected from 15 dug wells and analyzed for chromium species and other constituents. The results showed that the groundwater was relatively more oxidizing during post-monsoon periods than the pre-monsoon periods. Except one sample, the concentration of chromium species were found in the order of Cr(VI)>Cr(III)>Cr(III)-organic complexes during all the pre- and post-monsoon periods. In most of the wells, the concentrations of Cr(III), Cr(VI), and Cr(III)-organic decreased during post-monsoon periods compared to their pre-monsoon concentrations. However, the Cr(VI)/Cr_Total ratio still increased and the Cr(III)/Cr_Total ratio decreased during post-monsoon periods in most of the samples. The possible mechanisms for the temporal variation of chromium species were (1) Fe(II) reduction of Cr(VI) vs oxidation of Fe(II) by dissolved oxygen and (2) oxidation of Cr(III) by Mn(IV).     

Trace element concentration and speciation in selected urban soils in New York City

A long history of urbanization and industrialization has affected trace elements in New York City (NYC) soils. Selected NYC pedons were analyzed by aqua regia microwave digestion and sequential chemical extraction as follows: water soluble (WS); exchangeable (EX); specifically sorbed/carbonate bound (SS/CAR); oxide-bound (OX); organic/sulfide bound (OM/S). Soils showed a range in properties (e.g., pH 3.9 to 7.4). Sum of total extractable (SUM_TE) trace elements was higher in NYC parks compared to Bronx River watershed sites. NYC surface horizons showed higher total extractable (TE) levels compared to US non-anthropogenic soils. TE levels increased over 10 year in some of the relatively undisturbed and mostly wooded park sites. Surface horizons of park sites with long-term anthropogenic inputs showed elevated TE levels vs. subsurface horizons. Conversely, some Bronx River watershed soils showed increased concentrations with depth, reflective of their formation in a thick mantle of construction debris increasing with depth and intermingled with anthrotransported soil materials. Short-range variability was evident in primary pedons and satellite samples (e.g., Pb 253?±?143 mg/kg). Long-range variability was indicated by Pb_TE (348 versus 156 mg/kg) and Hg_TE (1 versus 0.3 mg/kg) concentrations varying several-fold in the same soil but in different geographic locations. Relative predominance of fractions: RES (37 %)?>?SS/CAR (22 %)?>?OX (20 %)?>?OM/S (10 %)?>?EX (7 %)?>?WS (4 %). WS and EX fractions were greatest for Hg (7 %) and Cd (14 %), respectively. RES was predominant fraction for Co, Cr, Ni, and Zn (41 to 51 %); SS/CAR for Cd and Pb (40 and 63 %); OM/S for Cu and Hg (36 and 37 %); and OX for As (59 %).