An assessment of sampling,preservation, and analytical procedures for arsenic speciation in potentially contaminated waters

This study was undertaken to ascertain optimal methods of sampling, preserving, separating, and analyzing arsenic species in potentially contaminated waters. Arsenic species are readily transformed in nature by slight changes in conditions. Each species has a different toxicity and mobility. The conventional field sampling method using filters of 0.45 μm in size could overestimate the dissolved arsenic concentrations, as passing suspended particles that can act as a sink or source of arsenic depending on the site condition. For arsenic species in neutral pH and iron-poor waters, the precipitation can be stable for up to 3 days without any treatment, but for longer periods, a preservative, such as phosphoric acid, is required. Also, the analytical procedure must be selected carefully because the levels and hydride generation efficiencies of arsenic in different species can vary, even for the same amount of arsenic. For arsenic speciation in samples that also include organic species, a hybrid high-performance liquid chromatography (HPLC) column and inductively coupled plasma mass spectrometry (ICP-MS) gave the best resolution and lowest detection limits. However, the procedure using a solid phase extraction (SPE) cartridge can be used economically and conveniently for analyzing samples containing only inorganic arsenic species, such as groundwater, especially that related to mine activity.     

Sulfur isotopic variations in soft tissues of five benthic animals from the reductive,tidal-flat sediments in northern Kyushu,Japan

The sulfur nutrition of five benthic animals living in or on reductive, tidal-flat sediments has been studied by using the sulfur isotopic signatures of their soft tissues. The mean '³⁴S values (+6.1‰ to +13.8‰, relative to the Cañyon Diablo troilite reference) of these animals' tissues are lower than those of many common marine animals, which have values close to those of seawater sulfate-sulfur (+21‰). This indicates that these animals use a ³⁴S-depleted sulfur source, which may be derived from bacterial sulfide in the sediments (less than -20‰). The animals that inhabit such sediments are adapted to an anoxic environment, where toxic hydrogen sulfide prevails. Due to the sulfide-rich habitat, benthic animals are expected to assimilate hydrogen sulfide directly during detoxification, or to prefer a diet which has a low '³⁴S signature. Variations in '³⁴S values of the sampled molluscs were fairly small, whereas migratory shrimp and fish tended to have larger variations, implying that migratory animals feed on diverse prey, while the molluscs feed on a common food, or their assimilative capacity for sulfide-sulfur does not vary among individuals. A gastropod inhabiting the surface of the reductive sediment showed a distinctively low '³⁴S value (+5.8‰ to +6.4‰), indicating that the animal fed on detritus from reeds and halophytes with low '³⁴S values (-19.1‰ to -2.1‰). This study suggests that some benthic animals incorporate sulfide-sulfur for their nutrition and that sulfur isotope composition can be a useful indicator in the analysis of the food habitat of animals.     

Contamination status of arsenic,lead, and cadmium of different wetland waters

The present investigation was conducted to determine the contamination status of arsenic (As), cadmium (Cd), and lead (Pb) in the wetland waters of Bhaluka in Bangladesh. Water samples were collected from 15 selected wetlands of Bhaluka region and analyzed using an atomic absorption spectrophotometer. Estimated results of three metals detected were As (7–80?µg?L^?1), Pb (0–86?µg?L^?1) and Cd (0–70?µg?L^?1) in water samples in all wetlands. The level of As in all investigated wetlands (93%) was higher than that of WHO recommended permissible limit of drinking water except Alanga wetland. However, As levels were higher than that recommended for livestock water quality levels. Eighty-seven percent of the investigated wetlands showed lower content of Pb than WHO recommended permissible limit of drinking water, but two wetland waters (Dohuria-1 and Chowdhuri) were polluted with higher Pb levels. Sixty-seven percent of the investigated wetlands displayed higher levels of Cd than WHO recommended permissible limit in drinking water. Dissolved organic material showed no significant difference among the 15 investigated wetlands water, but total dissolved solids was significantly greater. The condition of the water of all wetlands was basic pH. All water samples were applied to linear regression equation and correlation coefficients where values showed no significant differences. Data demonstrate that the estimated high metal concentrations of these ponds may contribute to bioaccumulation within plants, food grains and shrimp.     

Responses of fish assemblage structures to sandy beach types in Kyushu Island, southern Japan

To determine differences in fish assemblage structures between beach morphodynamic types on an exposed sandy shore, three beach types (reflective, intermediate, and dissipative) were sampled at Fukiagehama Beach, Kyushu Island, southern Japan, in May, August, and November 2006 and 2007. Distinct differences in physical conditions and the amount of major prey invertebrates, such as copepods, mysids, and amphipods, were recognized between the three beach types. The reflective beach was characterized mainly by turbulent swashes, coarse sediment, and a low abundance of major prey invertebrates. In contrast, the dissipative beach was characterized mostly by benign swashes, fine sediment, and a high abundance of prey invertebrates. The intermediate beach tended toward an intermediate condition between the reflective and dissipative beaches. The fish assemblage structures also differed clearly between the three beach types, with species and individual numbers being greatest on the dissipative beach and lowest on the reflective beach. A similarity index indicated differences in species composition of the assemblages between the beach types. Such differences arose primarily from the differential distributions of two dominant trophic groups, zooplankton (mostly copepods) and epibenthic crustacean (mainly mysids and amphipods) feeders, between the beach types, both groups tending to increase in species and individual numbers from the reflective beach to the dissipative beach. In addition, the mean standard length of all fish collected in each month tended to decrease toward the dissipative beach. These results suggested that beach types strongly influence sandy beach fish assemblage structures.     

Alkaline phosphatase activity in subtropical Central North Pacific waters using a sensitive fluorometric method

This paper describes a fluorometric method for assaying low levels of the enzyme alkaline phosphatase in seawater. The assay is based on the hydrolysis of the monophosphate ester bond of 3-0-methylfluorescein phosphate. This enzyme is synthesized by many microorganisms when phosphate becomes limiting. Alkaline phosphatase activity was detected in phytoplankton from the nutrient-impoverished surface waters of the subtropical Central North Pacific Ocean. The presence of naturally occurring phosphatase suggests that phosphorus may be limiting to phytoplankton growth in these waters. The phytoplankton in water samples lacking enzyme activity at the time of collection produced phosphatase within 1 to 2 days of incubation at in situ temperatures.     

The breeding cycles of two species of grapsid crabs (Crustacea: Decapoda) from the North Coast of Kyushu,Japan

The incidence of ovigerous females in populations of two grapsid crabs, Hemigrapsus penicillatus (de Haan, 1835) and Sesarma (Parasesarma) pictum (de Haan, 1835) were followed from August 1975 to November 1976. H. penicillatus, which inhabits the lower intertidal region near the mouth of Tatara-Umi Estuary, breeds from March to November. S. pictum, which inhibits crevices and abandoned holes of other species and is abundant at and above the upper intertidal region of the estuary, breeds from May to September. H. penicillatus matures when the female reaches 6 to 7 mm carapace width, whereas S. pictum becomes mature when the carapace width is 12 to 13 mm, although the maximum size attained by females of both species is almost the same. H. penicillatus produces 5 to 6 broods, S. pictum 2 to 3 broods, during a breeding season. The size of a newly laid egg of H. penicillatus is smaller than that of S. pictum. The number of eggs produced by a female H. penicillatus is greater than that of S. pictum during a breeding season. In both species the peak of the breeding season is during summer, at which time the ovarian activity is also apparently accelerated. The major environmental factor which controls the breeding in these crabs appears to be temperature. H. penicillatus is submerged at every high tide, and is relatively inactive from late November to February when the ambient water and air temperatures are rather low. S. pictum is dormant in crevices or understones of the splash zone from November to March. The length of the breeding season of these crabs appears to be inversely proportional to the period of their winter dormancy.     

Phycoerythrin and photosynthesis of the pelagic blue-green alga Trichodesmium thiebautii in the waters of Kuroshio,Japan

The photosynthetic function of phycoerythrin was investigated in the alga Trichodesmium thiebautii from the waters of Kuroshio, Japan. The spectroscopic characteristics of the in vivo and isolated T. thiebautii phycoerythrin pigments are identical, and have 3 absorption bands at 495, 547 and 562 nm. Light at the wavelengths corresponding to each absorption band of phycoerythrin is equally efficient in T. thiebautii photosynthesis, indicating that phycoerythrin is active in trapping light energy for photosynthesis. In the natural habitat, phycoerythrin is considered to be the main photosynthetic pigment in T. thiebautii photosynthesis.     

Microdistribution of the marine copepodOithona davisae in the shallow waters of Ariake-kai mud flats,Japan

The microdistribution ofOithona davisae Ferrari and Orsi inhabiting shallow waters of Ariake-kai, western Kyushu, Japan, was investigated in 1980–1981 by means of a pumping method. Water samples (10 l) were repeatedly collected from the surface to the bottom at intervals of 0.5 m. This species was dispersed when the tidal current ran fast (more than 20 cm s^–1), but aggregated in the upper layer during the period of slow current. Their density was highest when the current stopped. Aggregation ofO. davisae presumably induced the continuous flat swarm near the surface. It is to be expected that the shallow waters in Ariake-kai would be favorable as nursery grounds for the fish larvae and juveniles which depend on the presence of such swarms.Contribution no. 51 from the Aitsu Marine Biological Station     

A sensitive spectrophotometric method for the determination of arsenic in environmental samples

We developed a cost-effective and sensitive spectrophotometric method for the determination of arsenic at trace level using a new reagent, leuco malachite green. Here we show that, arsenic reacts with potassium iodate in acidic conditions to liberate iodine, and the liberated iodine selectively oxidizes leuco malachite green to malachite green dye. We studied the Beer’s law at 617 nm, which showed linearity over the concentration range 0.09–0.9 μg ml⁻¹ of arsenic. We show that the molar absorptivity, Sandell’s sensitivity and detection limit of the method are 6.1 × 10⁴ l mol⁻¹ cm⁻¹, 0.0012 μg cm⁻² and 0.025 μg ml⁻¹, respectively. We applied the developed method for the determination of arsenic in environmental samples.     

Evaluation of metabisulfite and a commercial steel wool for removing chromium(VI) from wastewater

Efficiency of metabisulfite and a commercial steel wool as reducing agents in the removal of Cr(VI) from wastewaters was evaluated. Chromium(VI) was converted to Cr(III), precipitated with NaOH, and removed by filtration. A reduction of more than 1.0 × 10⁵ and 4.0 × 10⁵ fold in total Cr and the Cr(VI) concentrations, respectively, was observed by employing steel wool masses as low as 0.4420 g to 30-mL solutions of wastewater. Chromium(III) hydroxide obtained after the treatment was recycled and used as marker in cattle nutrition studies. The liquid residue obtained after the treatment was reused as precipitation agent replacing NaOH.     

Logistic regression and fuzzy logic as a classification method for feral fish sampling sites

This study presents a classification method combining logistic regression and fuzzy logic in the determination of sampling sites for feral fish, Nile Tilapia (Tilapia rendalli). This method statistically analyzes the variable domains involved in the problem, by using a logistic regression model. This in turn generates the knowledge necessary to construct the rule base and fuzzy clusters of the fuzzy inference system (FIS) variables. The proposed hybrid method was validated using three fish stress indices; the Fulton Condition Factor (FCF) and the gonadossomatic and hepatossomatic indices (GSI and HSI, respectively), from fish sampled at 3 different locations in the Rio de Janeiro State. A multinomial logistic regression allowed for the FIS construction of the proposed method and both statistical approaches, when combined, complemented each other satisfactorily, allowing for the construction of an efficient classification method regarding feral fish sampling sites that, in turn, has great value regarding fish captures and fishery resource management.     

Physicochemical aspects of using natural scavengers in removing methylene blue (basic dye) from solution

Effluent from dyeing and finishing processes is an important source of water pollution. The effectiveness of bentonite, kaolinite and sediment from a local deposit in removing methylene blue as a cationic dye from aqueous solutions has been investigated. The adsorption equilibrium (isotherm) has been determined according to Freundlich and Langmuir equations. The optimum amount is 0.5 g for all adsorbents, and the optimum pH ranges are 2-8 for bentonite and 2-6 for kaolinite and sediment. With respect to kinetic modelling, the adsorption of methylene blue on various adsorbents was fitted to a second-order equation. Also, the thermodynamic parameters were determined. The negative free energy values indicate the feasibility of the process and spontaneous nature of adsorption. The positive ΔH° values indicate the endothermic nature of the process. Thus, Egyptian clay minerals and sediments have a great tendency to remove the dye from solutions.     

Physicochemical aspects of using natural scavengers in removing methylene blue (basic dye) from solution

Effluent from dyeing and finishing processes is an important source of water pollution. The effectiveness of bentonite, kaolinite and sediment from a local deposit in removing methylene blue as a cationic dye from aqueous solutions has been investigated. The adsorption equilibrium (isotherm) has been determined according to Freundlich and Langmuir equations. The optimum amount is 0.5 g for all adsorbents, and the optimum pH ranges are 2–8 for bentonite and 2–6 for kaolinite and sediment. With respect to kinetic modelling, the adsorption of methylene blue on various adsorbents was fitted to a second-order equation. Also, the thermodynamic parameters were determined. The negative free energy values indicate the feasibility of the process and spontaneous nature of adsorption. The positive ΔH° values indicate the endothermic nature of the process. Thus, Egyptian clay minerals and sediments have a great tendency to remove the dye from solutions.     

Characterization of arsenic content in marine organisms from temperate, tropical, and polar environments

Arsenic is a widely distributed element which occurs in several chemical forms in the marine environment. Inorganic arsenic mediates the most toxic effects and predominates in sea water and sediments, while organisms generally accumulate non-toxic organic forms to concentrations probably reflecting species-specific characteristics in arsenic metabolism. This work represents an additional contribution to our knowledge on natural levels and chemical speciation of arsenic in marine organisms; basal concentrations were characterized in several species (bivalves, crustaceans, and fishes) from different environments (polar, temperate, and tropical latitudes), and results revealed an elevated variability with values ranging from less than 5 to about 200 μg g^-1. No significant effects were observed as a function of the geographical area, with the only exception of crustaceans always showing more elevated arsenic concentrations in Mediterranean species (about 45-110 μg g^-1) compared with tropical species (lower than 30 μg g^-1). Chemical speciation of arsenic was investigated in representative species from the three studied taxa; the predominance of organic forms confirmed the general tendency of marine organisms to bioaccumulate non-toxic arsenic compounds, probably resulting from a detoxification pathway.     

Probability distributions of arsenic in soil from brownfield sites in Beijing (China): statistical characterization of the background populations and implications for site assessment studies

A probabilistic analysis was performed on soil arsenic concentration data from 4 brownfield sites at Beijing (Chaoyang and Haidian Districts), involved in environmental assessment studies. The available data sets were processed to provide a statistical characterization of the background populations and differentiate “anomalous data” from the natural range of variation of arsenic concentrations in soil. The site-specific background distributions and the existing wide-scale background values defined for the Beijing area were compared, discussing related implications for the definition of metal contamination soil screening levels (SSLs) in site assessment studies. The statistical analysis of As data sets discriminated site-specific background populations, encompassing 88% to 94% of the sample data, from outliers values, associated with either subsoil natural enrichments or possible anthropogenic releases. Upper Baseline Concentration (UBC) limits (+ 2σ level), including most of the site-specific metal background variability, were derived based on the statistical characterization of the background populations. Sites in the Chaoyang South District area had UBC values in the range 10.4–12.6 mg·kg^-1. These ranges provide meaningful SSL values to be adopted for As in local site assessment studies. Using the wide-scale background value for the Beijing area would have erroneously classified most of the areas in the subject sites as potentially contaminated.     

Mobilization of arsenic from technosols in a short-term dynamic column experiment

The release of arsenic from technosols was monitored using short-term dynamic leaching of homogeneous soil columns with native solution. Large amounts of readily available arsenic (16 mg kg^?1) were extracted from arsenic-rich ashy samples while representing less than 4 wt % of their total contents. In the first hour of leaching, the observed concentrations of water-soluble arsenic ranged from 650 to 830 μg L^?1, further increasing in the following leachates. The results showed that the concentrations of water-soluble arsenic were several times higher than the recommended limits for drinking water. Yet, most of arsenic is strongly bound to amorphous aluminosilicate phases. The contents of arsenic in the studied plant samples, including calculated transfer factors, confirmed that increased concentrations of arsenic in the soil of geological environment affected by dam failure of a coal ash pond may have a negative effect on crops since arsenic becomes part of the food chain.     

Toxicity of tri- and penta-valent arsenic, alone and in combination, to the cladoceran Daphnia carinata: the influence of microbial transformation in natural waters

The acute toxicity of arsenic(III) and arsenic(V) alone and in combination to a cladoceran, Daphnia carinata, was studied in both cladoceran culture medium and natural water collected from a local suburban stream. As(III) was found to be more toxic than As(V) to Daphnia survival. The LC₅₀ values for As(III), As(V), and As(III) + As(V) were 0.554, 1.499, and 0.692 mg l⁻¹, respectively. Although various species of As, particularly As(III) and As(V) co-exist together in natural waters, the existing guidelines for water quality are based on individual As species. The results of this investigation suggest that As(III) and As(V) can interact either synergistically or additively resulting in an increase in the overall toxicity of the mixture compared to individual As species. Also, indigenous microorganisms in natural water may play a significant role in the transformation of As, thereby influencing the toxicity of As in receiving waters. This study clearly suggests that the joint action of As species should be considered in the development of water quality guidelines. To our knowledge this is the first study on the interactive effect of As(III) and As(V) to a cladoceran. Thus, this study suggests that these two species of As, when present together above 0.1 mg l⁻¹ concentration, are toxic to fresh water invertebrates; therefore, pollution with these compounds may adversely affect natural ecosystems.     

电子废弃物拆解地水体多溴联苯醚分布特征

为了解和比较广东贵屿电子废弃物拆解地和珠三角城市地区水体中多溴联苯醚的种类、含量及分布特征,于2011年9月在广东贵屿周边地区和广州采集了20个地下水、7个地表水和4个珠江水,用反相C18萃取小柱提取净化后,利用气相色谱-质谱法测定了样品中的8种多溴联苯醚（PBDEs）。研究结果表明：贵屿地区地下水中PBDEs浓度总体上较高,总质量浓度范围为2.54~71.74 ng·L-1,平均为22.97 ng·L-1,各类PBDEs的检出率为25%~95%。三溴联苯醚（BDE28）、四溴联苯醚（BDE47）、五溴联苯醚（BDE99和BDE100之和）、六溴联苯醚（BDE153和BDE154之和）、七溴联苯醚（BDE183）和十溴联苯醚（BDE209）的质量浓度分布分别为nd~0.64、nd~18.43、nd~25.26、nd~13.92、nd~9.06和nd~15.60 ng·L-1。从物种上来看,分别源于四溴、五溴和十溴联苯醚产品的BDE47、BDE99和BDE209是贵屿地区地下水样中的优势同系物。通过比率P=（BDE47＋BDE99）/BDE209研究发现：低溴代联苯醚比高溴代联苯醚更易被地表径流迁移转换进入到地下水中。贵屿地区地表水中PBDEs的质量浓度范围为3.41~63.83 ng·L-1,平均总质量浓度为19.38 ng·L-1,稍低于当地地下水中PBDEs的平均总质量浓度,PBDEs的组成以高溴代的BDE209为特征,与世界其他水体研究结果相比,可以发现贵屿地区的地表水中PBDEs的平均总质量浓度明显偏高,说明该地区的地表水受到较严重的PBDEs污染,必须引起足够的重视。珠江水中PBDEs的总质量浓度范围为3.48~20.84 ng·L-1,平均为10.39 ng·L-1,表明近年来珠江水体中PBDEs污染有逐渐恶化的趋势。     

Concentration of arsenic in water, sediments and fish species from naturally contaminated rivers

Arsenic (As) may occur in surface freshwater ecosystems as a consequence of both natural contamination and anthropogenic activities. In this paper, As concentrations in muscle samples of 10 fish species, sediments and surface water from three naturally contaminated rivers in a central region of Argentina are reported. The study area is one of the largest regions in the world with high As concentrations in groundwater. However, information of As in freshwater ecosystems and associated biota is scarce. An extensive spatial variability of As concentrations in water and sediments of sampled ecosystems was observed. Geochemical indices indicated that sediments ranged from mostly unpolluted to strongly polluted. The concentration of As in sediments averaged 6.58 μg/g ranging from 0.23 to 59.53 μg/g. Arsenic in sediments barely followed (r = 0.361; p = 0.118) the level of contamination of water. All rivers showed high concentrations of As in surface waters, ranging from 55 to 195 μg/L. The average concentration of As in fish was 1.76 μg/g. The level of contamination with As differed significantly between species. Moreover, the level of bioaccumulation of As in fish species related to the concentration of As in water and sediments also differed between species. Whilst some fish species seemed to be able to regulate the uptake of this metalloid, the concentration of As in the large catfish Rhamdia quelen mostly followed the concentration of As in abiotic compartments. The erratic pattern of As concentrations in fish and sediments regardless of the invariable high levels in surface waters suggests the existence of complex biogeochemical processes behind the distribution patterns of As in these naturally contaminated ecosystems.