Trace elements in biodeposits and sediments from mussel culture in the Ria de Arousa (Galicia, NW Spain)

The trace elements present at highest concentrations were Cr and Zn, which probably originated from the dumping of effluent from a tanning factory. High proportions of these two elements were associated with the residual fraction. Biodeposits and sediments showed high concentrations of Cd and Pb in the reactive fraction, with a high proportion of the concentration in the reactive fraction being associated with carbonates. Nickel showed a higher degree of pyritization than the previous elements, although most of the Ni was associated with the residual and reactive fractions. Arsenic, Hg and Cu showed high degrees of pyritization, particularly below a depth of 5 cm. The results demonstrate that those elements with a high degree of pyritization may be released into the water through oxidation of the metal sulphides that they form when in suspension in oxic sea water, with the subsequent risk of increased bioavailability to benthic fauna.     

Heavy-metal pollution and arseniasis in Hetao region, China

In the Hetao region in northern China drinking water has become toxic due to the presence of arsenic (As) and other heavy metals in soil and water. The 7 counties in this region cover approx. 6100 km2, and in all 180,000 people are suffering from the toxic effects of contaminated drinking water. However, very few studies have been carried out in the region on the possible source of this arsenic. This paper is based on studies of the distribution of heavy metals in soil and groundwater. Results show that the average content of As is 0.483 microg g(-1) in groundwater and 13.74 microg g(-1) in soil. These levels are higher than the drinking water standard of 0.05 microg g(-1) recommended by the World Health Organization in 1984, and for the local background level in soil (5.20 microg g(-1)). This heavy-metal content in water and soil decreases gradually with increasing distance from the contaminated area, which fronts the Yin Mountains. The ratios of the Pb and Sr isotope contents in water are closely related to the ratios found in the water of the regions' mining area, and the ratios in soil correspond to the content of As in groundwater and soil in the area where pathological changes have been detected. Results suggest that the contaminants originate in the ore deposit zone fronting Yin mountains in the upper reaches of the Hetao Region.     

Arsenic speciation in plants growing in arsenic-contaminated sites

Concentrations of total arsenic and of arsenic species were determined by ICPMS and HPLC-ICPMS in terrestrial plant samples. The arsenic concentration in plant samples from the contaminated sites ranged from 1.14 to 98.5 mg kg(-1) (dry mass). However, a very high value, exceeding largely this range was found in a moss sample growing in the contaminated area (1750 mg kg(-1)). Plants growing in a non-contaminated area with similar geological characteristics contained 0.06-0.58 mg As kg(-1). Plant samples from different species were selected and extracted with water, water/methanol (9+1, v/v), and water/methanol (1+1, v/v). Water/methanol (9+1, v/v) was selected as extractant for the speciation analysis for all the plant samples. The extraction efficiencies ranged from 3.0% to 41.4%, with good agreement between samples from the same plant species. Arsenite and/or arsenate were found in all the plant samples. Additionally, methylarsonate (MA), dimethylarsinate (DMA), trimethylarsine oxide (TMAO) and tetramethylarsonium ion (TETRA) were also identified in several plants, and in some cases MA and DMA were the main species found. TMAO, which is usually found as a trace constituent in organisms, was also a significant arsenical in one of the studied samples, where it constituted 24% of the extracted arsenic. In the present study, the patterns of arsenic species varied with the plant species and much higher proportion of organoarsenicals was found in plants from the more contaminated sites.     

Environmental impact and recovery at two dumping sites for dredged material in the North Sea

The environmental impact and recovery associated with the long and uninterrupted disposal of large volumes of moderately contaminated dredged material from the port of Rotterdam was studied at nearby dumping sites in the North Sea. Observations were made on sediment contamination, ecotoxicity, biomarker responses and benthic community changes shortly after dumping at the 'North' site had ceased and at the start of disposal at the new dumping site 'Northwest'. During the period of dumping, very few benthic invertebrates were found at the North site. Concentrations of cadmium, mercury, polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and tributyltin (TBT) in the fine sediment fraction (<63 microm) from this site were 2-3 times higher than at the reference site. In four different bioassays with marine invertebrates the sediments showed no acute toxic effects. In tissue (pyloric caeca) of resident starfish Asterias rubens, residual levels of mercury, zinc, PCBs and dioxin-like activity were never more than twice those at the reference site. Four different biomarkers (DNA integrity, cytochrome P450 content, benzo[a]pyrene hydroxylase activity and acetylcholinesterase inhibition) were used on the starfish tissues, but no significant differences were found between North and the reference site. Minor pathological effects were observed in resident dab Limanda limanda. One year after dumping had ceased at the North site, a significant increase in the species richness and abundance of benthic invertebrates and a concomitant decrease in the fine sediment fraction of the seabed were observed. After 8.2 million m3 of moderately contaminated dredged material had been dumped at the new dumping site Northwest, the species richness and abundance of benthic invertebrates declined over an area extending about 1-2 km eastwards. This correlated with a shift in sediment texture from sand to silt. The contamination of the fine sediment fraction at the Northwest location doubled. It is concluded that marine benthic resources at and around the dumping sites have been adversely affected by physical disturbance (burial, smothering). However, no causal link could be established with sediment-associated contaminants from the dredged spoils.     

石灰沉淀法除砷的影响因素

以Ca(OH)2溶液为沉淀剂,处理模拟含砷废水砷酸钠溶液,考察了pH值、Ca/As摩尔比、自由沉降时间和反应温度等因素对石灰沉淀法除砷效果的影响。结果表明,在pH值为12,Ca/As摩尔比为6,沉降时间为48 h,反应温度为25℃时,石灰沉淀法除砷的效率可达到99.05%;此外,对高浓度的含砷废水,在石灰沉淀法除砷工艺中添加简单无机盐絮凝工艺,可显著降低出水总砷浓度,达到污水综合排放标准的要求。     

Environmental fate and bioavailability of wood preservatives in freshwater sediments near an old sawmill site.

Impacts of an old contaminated sawmill site located in Eastern Finland were studied, with emphasis on transportation and bioaccumulation of wood preservatives in the surrounding water system. To assess the transportation of chlorophenols and chromated copper arsenate (CCA) from the sawmill to the nearby lake, the concentrations of these compounds in selected sediment samples were analyzed. To assess the contribution of a pulp mill further upstream, the concentration of extractable organic halogens (EOX) was analyzed. Bioaccumulation of wood preservatives from sediments was examined using Lumbriculus variegatus as test organism. In sediments collected from the sawmill area, concentrations of chlorophenols, arsenic, chromium and copper were high. In the surrounding area the concentrations of these compounds were slightly elevated at some sampling points but were mostly within the natural range of variation. Thus, it can be concluded that transportation of wood preservatives from the sawmill area to its surroundings is fairly low. However, 60 microg/l of arsenic and 50 microg/l of copper were found in water taken from a brook that runs through a landfill area of the sawmill to the nearby river, and the concentration of arsenic in the surface sediment at one sampling point in the lake was slightly elevated. The total amount of organohalogens in sediment was higher in the river and the lake than in the sawmill area. Of all the wood preservatives studied, only arsenic was found to bioaccumulate in present conditions, reaching a tissue concentration of 362 microg/g dw in organisms exposed for 28 days to sediment from the brook. High concentration of arsenic in oligochaeta tissue was related to high concentration of arsenic in the pore water.     

Removal of arsenic from groundwater by granular titanium dioxide adsorbent

A novel granular titanium dioxide (TiO2) was evaluated for the removal of arsenic from groundwater. Laboratory experiments were carried out to investigate the adsorption capacity of the adsorbent and the effect of anions on arsenic removal. Batch experimental results showed that more arsenate [As(V)] was adsorbed on TiO2 than arsenite [As(III)] in US groundwater at pH 7.0. The adsorption capacities for As(V) and As(III) were 41.4 and 32.4 mgg(-1) TiO2, respectively. However, the adsorbent had a similar adsorption capacity for As(V) and As(III) (approximately 40 mgg(-1)) when simulated Bangladesh groundwater was used. Silica (20 mgl(-1)) and phosphate (5.8 mgl(-1)) had no obvious effect on the removal of As(V) and As(III) by TiO2 at neutral pH. Point-of-entry (POE) filters containing 3 l of the granular adsorbent were tested for the removal of arsenic from groundwater in central New Jersey, USA. Groundwater was continuously passed through the filters at an empty bed contact time (EBCT) of 3 min. Approximately 45,000 bed volumes of groundwater containing an average of 39 microgl(-1) of As(V) was treated by the POE filter before the effluent arsenic concentration increased to 10 microgl(-1). The total treated water volumes per weight of adsorbent were about 60,000 l per 1 kg of adsorbent. The field filtration results demonstrated that the granular TiO2 adsorbent was very effective for the removal of arsenic in groundwater.     

Aquatic arsenic: phytoremediation using floating macrophytes

Phytoremediation, a plant based green technology, has received increasing attention after the discovery of hyperaccumulating plants which are able to accumulate, translocate, and concentrate high amount of certain toxic elements in their above-ground/harvestable parts. Phytoremediation includes several processes namely, phytoextraction, phytodegradation, rhizofiltration, phytostabilization and phytovolatilization. Both terrestrial and aquatic plants have been tested to remediate contaminated soils and waters, respectively. A number of aquatic plant species have been investigated for the remediation of toxic contaminants such as As, Zn, Cd, Cu, Pb, Cr, Hg, etc. Arsenic, one of the deadly toxic elements, is widely distributed in the aquatic systems as a result of mineral dissolution from volcanic or sedimentary rocks as well as from the dilution of geothermal waters. In addition, the agricultural and industrial effluent discharges are also considered for arsenic contamination in natural waters. Some aquatic plants have been reported to accumulate high level of arsenic from contaminated water. Water hyacinth (Eichhornia crassipes), duckweeds (Lemna gibba, Lemna minor, Spirodela polyrhiza), water spinach (Ipomoea aquatica), water ferns (Azolla caroliniana, Azolla filiculoides, and Azolla pinnata), water cabbage (Pistia stratiotes), hydrilla (Hydrilla verticillata) and watercress (Lepidium sativum) have been studied to investigate their arsenic uptake ability and mechanisms, and to evaluate their potential in phytoremediation technology. It has been suggested that the aquatic macrophytes would be potential for arsenic phytoremediation, and this paper reviews up to date knowledge on arsenic phytoremediation by common aquatic macrophytes.     

Arsenic hyperaccumulation by Pteris vittata from arsenic contaminated soils and the effect of liming and phosphate fertilisation

Pot experiments were carried out to investigate the potential of phytoremediation with the arsenic hyperaccumulator Pteris vittata in a range of soils contaminated with As and other heavy metals, and the influence of phosphate and lime additions on As hyperaccumulation by P. vittata. The fern was grown in 5 soils collected from Cornwall (England) containing 67-4550 mg As kg(-1) and different levels of metals. All soils showed a similar distribution pattern of As in different fractions in a sequential extraction, with more than 60% of the total As being associated with the fraction thought to represent amorphous and poorly-crystalline hydrous oxides of Fe and Al. The concentration of As in the fronds ranged from 84 to 3600 mg kg(-1), with 0.9-3.1% of the total soil As being taken up by P. vittata. In one soil which contained 5500 mg Cu kg(-1) and 1242 mg Zn kg(-1), P. vittata suffered from phytotoxicity and accumulated little As (0.002% of total). In a separate experiment, neither phosphate addition (50mg P kg(-1) soil) nor liming (4.6 g CaCO3 kg(-1) soil) was found to affect the As concentration in the fronds of P. vittata, even though phosphate addition increased the As concentration in the soil pore water. Between 4 and 7% of the total soil As was taken up by P. vittata in 4 cuttings in this experiment. The results indicate that P. vittata can hyperaccumulate As from naturally contaminated soils, but may be suitable for phytoremediation only in the moderately contaminated soils.     

A global health problem caused by arsenic from natural sources

Arsenic is a carcinogen to both humans and animals. Arsenicals have been associated with cancers of the skin, lung, and bladder. Clinical manifestations of chronic arsenic poisoning include non-cancer end point of hyper- and hypo-pigmentation, keratosis, hypertension, cardiovascular diseases and diabetes. Epidemiological evidence indicates that arsenic concentration exceeding 50 microg l(-1) in the drinking water is not public health protective. The current WHO recommended guideline value for arsenic in drinking water is 10 microg l(-1), whereas many developing countries are still having a value of 50 microg l(-1). It has been estimated that tens of millions of people are at risk exposing to excessive levels of arsenic from both contaminated water and arsenic-bearing coal from natural sources. The global health implication and possible intervention strategies were also discussed in this review article.     

Removal of hexafluoroarsenate from waters

Arsenic predominantly occurs in natural ground and surface waters as arsenate and arsenite. Other arsenic species can also be present in anthropogenically influenced waters. By means of a newly-developed speciation technique an arsenic compound was identified as hexafluoroarsenate at high concentration (about 0.8mgl(-1) as As) in a lake polluted by waste water from a former crystal glass factory. This compound shows a completely different behavior than common arsenite and arsenate in waters. However, respective literature data were little found regarding its environmental behavior as well as the applicable remediation technologies. Conventional arsenic treatment mechanisms, such as the well-known sorption to iron hydroxides, can not be used to remediate water with this compound. Hence, an effective method to remove hexafluoroarsenate from water was developed using its strong affinity to anion exchangers (strong basic exchangers with quaternary ammonium groups). The sorption can be described by a Langmuir isotherm and first-order kinetics with a half-life of about 10min. Interferences by sulphate and fluoride, present at much higher concentrations in the polluted lake water, might be expected due to the anion exchange mechanism, but were shown to be of minor importance.     

Acid mine drainage arising from gold mining activity in Johannesburg,South Africa and environs

The Witwatersrand region of South Africa is famous for its gold production and a major conurbation, centred on Johannesburg, has developed as a result of mining activity. A study was undertaken of surface and ground water in a drainage system in this area. Soils were also analysed from a site within the mining district. This study revealed that the ground water within the mining district is heavily contaminated and acidified as a result of oxidation of pyrite (FeS2) contained within mine tailings dumps, and has elevated concentrations of heavy metals. Where the water table is close to surface, the upper 20 cm of soil profiles are severely contaminated by heavy metals due to capillary rise and evaporation of the ground water. The polluted ground water is discharging into streams in the area and contributes up to 20% of stream discharge, causing a lowering of pH of the stream water. Much of the metal load is precipitated in the stream: Fe and Mn precipitate as a consequence of oxidation, while other heavy metals are being removed by co-precipitation. The oxidation of iron has created a redox buffer which controls the pH of the stream water. The rate of oxidation and of dilution is slow and the deleterious effect of the addition of contaminated water persists for more than 10 km beyond the source.     

Arsenic accumulation by two brake ferns growing on an arsenic mine and their potential in phytoremediation

In an area near an arsenic mine in Hunan Province of south China, soils were often found with elevated arsenic levels. A field survey was conducted to determine arsenic accumulation in 8 Cretan brake ferns (Pteris cretica) and 16 Chinese brake ferns (Pteris vittata) growing on these soils. Three factors were evaluated: arsenic concentration in above ground parts (fronds), arsenic bioaccumulation factor (BF; ratio of arsenic in fronds to soil) and arsenic translocation factor (TF; ratio of arsenic in fronds to roots). Arsenic concentrations in the fronds of Chinese brake fern were 3-704 mg kg-1, the BFs were 0.06-7.43 and the TFs were 0.17-3.98, while those in Cretan brake fern were 149-694 mg kg-1, 1.34-6.62 and 1.00-2.61, respectively. Our survey showed that both ferns were capable of arsenic accumulation under field conditions. With most of the arsenic being accumulated in the fronds, these ferns have potential for use in phytoremediation of arsenic contaminated soils.     

Stabilisation of MSWI bottom ash with sulphide-rich anaerobic effluent

Effluent of an anaerobic sulphate-reducing wastewater treatment process was used to stabilise bottom ash. The effect of stabilisation on the concentration and binding of Ca, P, S, Cu, Pb, Zn, As, Cr, and Mo were studied by comparing results of sequential extraction from fresh and stabilised bottom ash. The stabilisation treatment improved the retention of Ca, Cu, Pb, S, and Zn in bottom ash compared to a treatment with ion-exchanged water. In addition to retention, Cu, S, and Zn were accumulated from the anaerobic effluent in the bottom ash. Concentrations of As, Cr, and Mo remained on the same level, whereas leaching of P increased compared to control treatment with ion-exchanged water. Improved retention and accumulation were the result of increased binding to less soluble fractions. The highest increases were in the sulphide and organic carbon bound fraction and in the carbonate fraction. Enhanced carbonation was probably due to CO2 deriving from the degradation of organic carbon. Flushing of stabilised bottom ash with ion-exchanged water ensured that the observed changes were not easily reversed. Most of the sulphide in the anaerobic effluent was removed when it was passed through bottom ash. The objective was to study the feasibility of sulphide-rich anaerobic effluent in bottom ash stabilisation and changes in the binding of the elements during stabilisation. In addition, the ability of the process to remove sulphide from the effluent was observed.     

Environmental contamination with polychlorinated biphenyls in the area of their former manufacture in Slovakia

Evidently increased environmental pollution as a consequence of the 25-year manufacture of polychlorinated biphenyls (PCBs) in eastern Slovakia was observed. PCB levels determined in ambient air, soil, surface water, bottom sediment, wildlife (fish and game) samples collected in a potentially contaminated area of about 250 km2 (a part of the Michalovce district) were compared with those determined in a control area (Stropkov district). Up to 1700 ng/m3 were found in ambient air in a village close to a manufacturer's dumping site and a highly contaminated manufacturer's effluent canal whereas PCB concentrations in ambient air samples taken in villages in the control area were about 80 ng/m3 only. While soil samples taken from the agricultural fields of the polluted area contained PCBs at levels comparable with soil samples from the control area (about 0.008 mg/kg) much higher values (from 0.4 to 53,000 mg/kg) were determined in soil taken in the vicinity of manufacturer's landfill and storage sites and especially plants preparing asphalted gravel using formerly PCBs in their heat-exchanging systems. The contamination of the Laborec river and large Zemplinska Sirava reservoir is caused by the manufacturer's effluent canal since PCB levels in the canal sediment are still to be found about 3000 mg/kg. While PCB levels in sediment samples from Michalovce watercourses ranged between 1.7 and 6 mg/kg, sediment samples from the control Stropkov district ranged between 0.007 and 0.052 mg/kg only. Fish living in contaminated Michalovce waters contained about hundred times higher PCB levels than those caught in Stropkov ones. Similarly, game animals shot in Michalovce forests contained several times higher levels than those shot in Stropkov ones.     

Chemical reactions of uranium in ground water at a mill tailings site

We studied soil and ground water samples from the tailings disposal site near Tuba City, AZ, located on Navajo sandstone, in terms of uranium adsorption and precipitation. The uranium concentration is up to 1 mg/l, 20 times the maximum concentration for ground water protection in the United States. The concentration of bicarbonate (HCO₃⁻) in the ground water increased from ≤7×10⁻⁴ M, the background concentration, to 7×10⁻³ M. Negatively charged uranium carbonate complexes prevail at high carbonate concentrations and uranium is not adsorbed on the negatively charged mineral surfaces. Leaching experiments using contaminated and uncontaminated sandstone and 1 N HCl show that adsorption of uranium from the ground water is negligible. Batch adsorption experiments with the sandstone and ground water at 16°C, the in situ ground water temperature, show that uranium is not adsorbed, in agreement with the results of the leaching experiments. Adsorption of uranium at 16°C is observed when the contaminated ground water is diluted with carbonate-free water. The observed increase in pH from 6.7 to 7.3 after dilution is too small to affect adsorption of uranium on the sandstone. Storage of undiluted ground water to 24°C, the temperature in the laboratory, causes coprecipitation of uranium with aragonite and calcite. Our study provides knowledge of the on-site uranium chemistry that can be used to select the optimum ground water remediation strategy. We discuss our results in terms of ground water remediation strategies such as pump and treat, in situ bioremediation, steam injection, and natural flushing.     

Arsenic mobility in contaminated lake sediments

An arsenic contaminated lake sediment near a landfill in Maine was used to characterize the geochemistry of arsenic and assess the influence of environmental conditions on its mobility. A kinetic model was developed to simulate the leaching ability of arsenic in lake sediments under different environmental conditions. The HM1D chemical transport model was used to model the column experiments and determine the rates of arsenic mobility from the sediment. Laboratory studies provided the information to construct a conceptual model to demonstrate the mobility of arsenic in the lake sediment. The leaching ability of arsenic in lake sediments greatly depends on the flow conditions of ground water and the geochemistry of the sediments. Large amounts of arsenic were tightly bound to the sediments. The amount of arsenic leaching out of the sediment to the water column was substantially decreased due to iron/arsenic co-precipitation at the water-sediment interface. Overall, it was found that arsenic greatly accumulated at the ground water/lake interface and it formed insoluble precipitates.     

Uptake and accumulation behaviour of angiosperms irrigated with solutions of different arsenic species

Uptake and metabolisation of arsenic as a function of both the plant type and the chemical form of arsenic were examined. For this purpose two different plant species (Silene vulgaris and Plantago major) were selected that differed in their vitality and accumulation behaviour on arsenic-loaded substrates. The plants were cultivated on soil and irrigated with aqueous solutions of an inorganic arsenic compound (arsenious acid) and an organic compound (dimethylarsinate). The arsenic species accumulated in the parts of the plants above ground were extracted by PLE and determined using IC-ICP-MS. The concentrations and metabolisation products of arsenic found in the extracts indicate different mechanisms of arsenic uptake and transformation in both angiosperms. The arsenic species pattern showed that S. vulgaris was more arsenic--tolerable than P. major which is attributed to a low arsenate to arsenite concentration ratio in the plant compartments. S. vulgaris was also able to demethylate and reduce dimethylarsinate to form arsenite in a high extent. P. major accumulated only eight times lower concentration of arsenic, and the arsenate to arsenite concentration ratio shifted to higher values. Metabolisation products of dimethylarsinate did not occur under the present experimental conditions. The vitality of the angiosperms seems to be very dependent on the ability of the plant to reduce arsenate to arsenite.     

The oxidation states of arsenic in well-water from a chronic arsenicism area of northern Mexico

Aquifers in the Región Lagunera in northern Mexico are heavily contaminated with arsenic. The range of total arsenic concentrations in 128 water samples analyzed was 0.008 to 0.624 mg litre(-1), and concentrations greater than 0.05 mg litre(-1) were found in 50% of them. Approximately 400 000 people living in rural areas were exposed to high As concentrations. Most of the As was in inorganic form and pentavalent arsenic [As(V)] was the predominant species in 93% of the samples. In 36% of the samples, however, variable percentages (20-50) of trivalent As [As(III)] were found. Organic arsenicals were present in very small amounts. Since As(III) is several times more toxic than As(V), we suggest that periodic studies be performed on the As(III)/As(V) ratio in wells whose total As concentrations are above 0.05 mg litre(-1), in combination with epidemiological studies to evaluate possible differences in health effects produced by different As species.     

Feasibility of using metals to remediate water containing TCE

The feasibility of treating underground water contaminated by a chlorinated organic compound with bimetallics Fe/Ni, Zn/Ni and Zn single metal was studied. Column tests to simulate a reactive permeable wall in a funnel-and-gate system were used. Research results indicated that bimetallic Fe⁰/Ni⁰ and Zn⁰/Ni⁰ all had a very strong degraded power to trichloroethylene (TCE ) at concentration up to 25 mg/l under different flow rates (27 cm/day–20 m/day). Furthermore, the concentrations of TCE and various ions in the treated effluent were nearly lower than the values specified in related standards for drinking water in Taiwan. These results showed that this technique could be effectively and safely used as an underground water remediation process.