Leaching of copper and zinc from spent antifouling paint particles

Leaching of Cu and Zn from a composite of spent antifouling paint particles, containing about 300 mg g⁻¹ and 110 mg g⁻¹ of the respective metals, was studied in batch experiments. For a given set of simulated environmental conditions, release of Cu was independent of paint particle concentration due to attainment of pseudo-saturation, but Zn was less constrained by solubility effects and release increased with increasing particle concentration. Leaching of Cu increased but Zn decreased with increasing salinity, consistent with mechanisms governing the dissolution of Cu₂O in the presence of chloride and Zn acrylates in the presence of seawater cations. Because of complex reaction kinetics and the presence of calcium carbonate in the paint matrix, metal leaching appeared to be greater at 4 °C than 19 °C under many conditions. These findings have important environmental and biological implications regarding the deliberate or inadvertent disposal of antifouling paint residues.     

Can we remove iodine-131 from tap water in Japan by boiling? - Experimental testing in response to the Fukushima Daiichi Nuclear Power Plant accident

Iodine-131 concentrations in tap water higher than 100 Bq L⁻¹ were reported by several local governments in Japan following the Fukushima Daiichi Nuclear Power Plant accident. Some individuals in the emergency-response community recommended the boiling of tap water to remove iodine-131. However, the tap water boiling tests in this study showed no iodine-131 loss from the tap water with either short-term boiling (1-10 min) or prolonged boiling (up to 30 min) resulting in up to 3-fold volume reductions. In this situation, boiling was shown to be not effective in removing iodine-131 from tap water; indeed even higher concentrations may result from the liquid-volume reduction accompanying this process.     

Bioaccessibility of metals in soils and dusts contaminated by marine antifouling paint particles

Fragments of antifouling paint and environmental geosolids have been sampled from the island of Malta and analysed for total and bioaccessible metals. Total concentrations of Ba, Cd, Cu, Pb, Sn and Zn were two to three orders of magnitude higher in spent antifouling composites relative to respective values in background soils and road dusts. Paint fragments were visible in geosolids taken from the immediate vicinity of boat maintenance facilities and mass balance calculations, based on Ba as a paint tracer, suggested that the most contaminated soils, road dusts and boatyard dusts contained about 1%, 7% and 9%, respectively, of antifouling particles. Human bioaccessibilities of metals were evaluated in selected samples using a physiologically based extraction technique. Accessibilities of Cd, Cu, Pb and Zn in the most contaminated solids were sufficient to be cause for concern for individuals working in the boat repair industry and to the wider, local community.     

Speciation distribution and mass balance of copper and zinc in urban rain, sediments, and road runoff

Heavy metal pollution in road runoff had caused widespread concern since the last century. However, there are little references on metal speciation in multiple environmental media (e.g., rain, road sediments, and road runoff). Our research targeted the investigation of metal speciation in rain, road sediments, and runoff; the analysis of speciation variation and mass balance of metals among rain, road sediments, and runoff; the selection of main factors by principal component analysis (PCA); and the establishment of equation to evaluate the impact of rain and road sediments to metals in road runoff. Sequential extraction procedure contains five steps for the chemical fractionation of metals. Flame atomic absorption spectrometry (Shimadzu, AA-6800) was used to determine metal speciation concentration, as well as the total and dissolved fractions. The dissolved fractions for both Cu and Zn were dominant in rain. The speciation distribution of Zn was different from that of Cu in road sediments, while speciation distribution of Zn is similar to that of Cu in runoff. The bound to carbonates for both Cu and Zn in road sediments were prone to be dissolved by rain. The levels of Cu and Zn in runoff were not obviously influenced by rain, but significantly influenced by road sediments. The masses for both Cu and Zn among rain, road sediments, and road runoff approximately meet the mass balance equation for all rainfall patterns. Five principal factors were selected for metal regression equation based on PCA, including rainfall, average rainfall intensity, antecedent dry periods, total suspended particles, and temperature. The established regression equations could be used to predict the effect of road runoff on receiving environments.     

Leaching of hydrophobic Cu and Zn from discarded marine antifouling paint residues: Evidence for transchelation of metal pyrithiones

Leaching of Cu and Zn from a composite of discarded antifouling paint residues ([Cu] = 288 mg g⁻¹; [Zn] = 96 mg g⁻¹) into natural sea water has been studied over a period of 75 h. Total Cu and Zn were released according to a pseudo first-order reaction, with rate constants on the order of 0.3 and 2.5 (mg L⁻¹)⁻¹ h⁻¹, respectively, and final concentrations equivalent to the dissolution of about 8 and 2% of respective concentrations in the composite. Time-distributions of hydrophobic metals, determined by solid phase extraction-methanol elution, were more complex. Net release of hydrophobic Cu was greater in the absence of light than under a sequence of light-dark cycles; however, hydrophobic Zn release was not detected under the former conditions but contributed up to 50% of total aqueous Zn when light was present. These observations are interpreted in terms of the relative thermodynamic and photolytic stabilities of biocidal pyrithione complexes.     

Zamzam water: concentration of trace elements and other characteristics

Many Muslims drink Zamzam water for use either medicinally or religiously. Millions of pilgrims drink it and take bottles of it to their home countries. Heated scientific and political debates appeared after BBC reported in May 2011 that Zamzam water is poisonous, because of the high levels of arsenic. The World Health Organizations classifies arsenic as a human carcinogen, but some types of arsenic are also used as medicines. Adequate scientific studies on the Zamzam water are absent. This paper will provide, for the first time, basic and comprehensive information regarding the geochemical properties of Zamzam water for more than 30 indicators and using the state-of-the-art laboratory facilities. The data will help us to understand the sources of pollution under discussion, reactions at both local and international levels; and will highlight the potential healing capacity of Zamzam water. Thirty Zamzam water samples were collected by three distinct methods; from 10 pilgrims living in different locations in Germany in 2007, 10 samples from shops in Frankfurt and Berlin in 2011, and 10 samples directly from Makkah in 2011. The samples were analyzed 2 weeks after collection for more than 30 indicators: pH, EC, Eh, Cl, F, Br, NO₃, PO₄, SO₄, HCO₃, Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn beside others. Four major instruments were used; the IC, the ICPOES, the ICPMS and the HGAAS. The quality of the water did not change for 2 years and there was an excellent agreement among the results of the 30 water samples as well as between the results of the 2 years for the same samples analyzed in 2007 and 2008. The water is alkaline (average pH is 8) with an average Li concentration of 15 μg L⁻¹. The average concentrations of As and NO₃ showed values three times higher than the WHO standards (27 μg L⁻¹ and 150 mg L⁻¹, respectively). The averages of Ca and K were 95 and 50 mg L⁻¹, respectively. Very urgent steps are required to scientifically screen for the elevated parameters As, NO₃, Ca, and K in all Zamzam water sources and locations with full transparency. The resultant information should be made available to the public, and the relationship between pollution and human health should be addressed. The alkalinity of Zamzam water and the presence of trace amounts of As and Li may cause the healing power. However, a scientific strategy should be developed and adopted to enable further research and studies on toxicology and treatment technologies could be applied if needed.     

Accumulation of Cu and Zn from antifouling paint particles by the marine macroalga,Ulva lactuca

The marine macroalga, Ulva lactuca, has been exposed to different concentrations of antifouling paint particles (4–200 mg L^?1) in the presence of a fixed quantity of clean estuarine sediment and its photosynthetic response and accumulation of Cu and Zn monitored over a period of 2 days. An immediate (<2 h) toxic effect was elicited under all experimental conditions that was quantitatively related to the concentration of contaminated particles present. Likewise, the rate of leaching of both Cu and Zn was correlated with the concentration of paint particles added. Copper accumulation by the alga increased linearly with aqueous Cu concentration, largely through adsorption to the cell surface, but significant accumulation of Zn was not observed. Thus, in coastal environments where boat maintenance is practiced, discarded antifouling paint particles are an important source of Cu, but not Zn, to U. lactuca.     

Effects of biochar and the earthworm Eisenia fetida on the bioavailability of polycyclic aromatic hydrocarbons and potentially toxic elements

Polycyclic aromatic hydrocarbons (PAHs) and potentially toxic elements (PTEs) were monitored over 56 days in calcareous contaminated-soil amended with either or both biochar and Eisenia fetida. Biochar reduced total (449 to 306 mg kg⁻¹) and bioavailable (cyclodextrin extractable) (276 to 182 mg kg⁻¹) PAHs, PAH concentrations in E. fetida (up to 45%) but also earthworm weight. Earthworms increased PAH bioavailability by >40%. Combined treatment results were similar to the biochar-only treatment. Earthworms increased water soluble Co (3.4 to 29.2 mg kg⁻¹), Cu (60.0 to 120.1 mg kg⁻¹) and Ni (31.7 to 83.0 mg kg⁻¹) but not As, Cd, Pb or Zn; biochar reduced water soluble Cu (60 to 37 mg kg⁻¹). Combined treatment results were similar to the biochar-only treatment but gave a greater reduction in As and Cd mobility. Biochar has contaminated land remediation potential, but its long-term impact on contaminants and soil biota needs to be assessed.     

Constructed wetlands as a component of the agricultural landscape: mitigation of herbicides in simulated runoff from upland drainage areas

Constructed wetlands are a recommended practice for buffering pollutant source areas and receiving waters. A wetland consisting of a sediment trap and two treatment cells was constructed in a Mississippi Delta lake watershed. A 3-h simulated runoff event was initiated (2003) to evaluate fate and transport of atrazine and fluometuron through the wetland. Water samples were collected during a runoff simulation and then afterward at selected intervals for 21 d, and analyzed for the herbicides. Breakthrough patterns for herbicide concentrations in water samples during the first 20 h after simulated runoff showed peak concentrations in the first 6 h, with gradual tailing as the herbicide pulse was diluted in the second, excavated (deeper) cell. Atrazine and fluometuron concentrations in the first (shallower, non-excavated) cell averaged 12- and 20-fold greater, respectively, than those in the second cell following simulated runoff, indicating entrapment in the first cell. Atrazine and fluometuron concentrations in the shallower cell decreased 32% and 22%, respectively, 9 d following simulated runoff, indicating either degradation or sorption to soil or wetland flora. In the excavated cell, concentrations were even lower, and atrazine declined more rapidly than fluometuron. Results indicate constructed wetlands can improve downstream water quality though sequestration or processing of pollutants.     

Runoff effect on eutrophic lake water quality and heavy metal distribution in recent littoral sediment

Multivariate statistical methods (hierarchical clustering analysis: HCA, and principal component analysis: PCA) were used to study the influence of runoff and other diffuse pollution sources on lake water chemistry of Hough Park lake in Central Missouri. In addition, heavy metal concentrations in lake littoral sediment were evaluated for enrichment and probable ecological risk. The abundance of macronutrients in the lake water column followed the order: Ca > Mg > TIC > K > Na > S > NO₃ - N > Fe > NH₃ - N > TP. Heavy metal concentrations in the lake water column were below acute and chronic level ecological guidelines. TN:TP ratios (range: 4.1-6.8) revealed nitrogen limitation of algal and other photosynthetic plant growth. The HCA showed two major clusters of similarity between the sampling points suggesting different pollution levels for the clusters. PCA 1, 2 and 3 reflected the influence of natural biochemical processes, atmospheric deposition and runoff respectively on lake water chemistry. The abundance of heavy metals and the normalizing element (Li) in littoral sediment (<63 μm fraction) samples analyzed in decreasing order were: Mn > Zn > Cr > Ni > Li > Cu > Pb > Cd > Hg. The average concentration of Cr, Mn and Ni in littoral sediment fraction exceeded the respective lowest effects level (LEL) threshold limit. Metal bioavailability in sediment fraction was low since the most labile metal species contained between 0% and 11% of the total metal content. Using the risk assessment code (RAC) criteria, only Mn posed a medium risk to the lake system.     

Thallium in the hydrosphere of south west England

Thallium is a highly toxic metal whose environmental concentrations, distributions and behaviour are not well understood. In the present study we measure the concentrations of Tl in filtered and unfiltered samples of rain, tap, river, estuarine and waste waters collected from south west England. Dissolved Tl was lowest (<20 ng L⁻¹) in tap water, rain water, treated sewage and landfill effluents, estuarine waters, and rivers draining catchments of sandstones and shales. Concentrations up to about 450 ng L⁻¹ were observed in rivers whose catchments are partly mineralized and where metal mining was historically important, and the highest concentration (∼1400 ng L⁻¹) was measured in water abstracted directly from an abandoned mine. Compared with other trace metals measured (e.g. As, Cd, Co, Cr, Cu, Ni, Pb, Zn), Tl has a low affinity for suspended particles and undergoes little removal by conventional (hydroxide precipitation) treatment of mine water.     

Processing of antifouling paint particles by Mytilus edulis

Particles of spent antifouling paint collected from a marine boatyard were ground and subsequently administered to the filter-feeding bivalve, Mytilus edulis, maintained in static aquaria. Concentrations of Cu and Zn were measured in seawater throughout a 16 h feeding phase and a 24 h depuration phase, in rejected and egested particles collected during the respective phases, and in the organisms themselves at the end of the experiments. Concentrations and distributions of Cu and Zn in processed particles indicated that M. edulis was able to ingest paint particles, regardless of whether nutritionally viable silt was present, and no mechanism of particle discrimination was evident. Enrichment of Cu and Zn in the visceral mass of individuals and in the aqueous phase during depuration supported these assertions, although elevated concentrations in other compartments of the organism (e.g. shell, gill) suggested that biotic and abiotic uptake of aqueous metal was also important.     

Leaching of zinc from tire wear particles under simulated estuarine conditions

Tire wear particles (TWP) abraded from end-of-life passenger car tires have been added at a concentration of 1 g L⁻¹ to river water, sea water and mixtures thereof in order to examine the chemical controls on the leaching of Zn from the rubber matrix. Results of time-dependent experiments conducted over a period of 5 days were consistent with a diffusion controlled leaching mechanism with rate constants of about 0.04 mg L⁻¹ h^−1/2 in river water and between about 0.02 and 0.03 mg L⁻¹ h^−1/2 in sea water. Additional experiments revealed a reduction in Zn dissolution with both increasing salinity and pH and enhancement of leaching in the presence of fluorescent light compared with dark conditions. In corresponding experiments conducted in the presence of a fixed quantity (0.8 g L⁻¹) of clean, fractionated estuarine sediment, aqueous Zn concentrations were reduced by at least an order of magnitude. Increasing the quantity of sediment resulted in a progressive reduction in Zn concentration until an apparent equilibrium was achieved, with partition coefficients defining the sediment-water distribution of Zn of about 550 mL g⁻¹ and 270 mL g⁻¹ in river water and sea water, respectively. Results are interpreted in terms of the dissolution of ZnO and other residual complexes from the matrix and the subsequent, rapid adsorption of Zn²⁺ ions to coexistent estuarine sediment. The findings of the study are discussed in terms of their implications for the transport, fate and effects of TWP Zn in aquatic environments that are likely to receive urban runoff.     

Cadmium speciation and accumulation in periphyton in a small stream with dynamic concentration variations

Accumulation of cadmium in periphyton was investigated under field conditions while Cd concentration and speciation were dynamically varying in a small stream during rain events. Speciation in water was determined in situ by diffusion gradient in thin-films (DGT) and by modeling of complexation with fulvic acids. During the rain events, dissolved Cd concentrations increased from 0.17 nM to 0.27-0.36 nM, and 70-97% were DGT-labile. Cd content in periphyton closely followed Cd concentrations in water, despite higher concentrations of Zn and Mn, and may be controlled by either free or DGT-labile Cd concentrations. Decrease of Cd content in periphyton after the rain events was slower than the decrease of Cd concentration in water. Concentrations of Zn, Mn, Cu, Pb and Fe in periphyton also followed the dynamic variations of metal concentrations in water. Repeated exposure of periphyton to elevated dissolved Cd may lead to Cd accumulation.     

The potential of willow for remediation of heavy metal polluted calcareous urban soils

Growth performance and heavy metal uptake by willow (Salix viminalis) from strongly and moderately polluted calcareous soils were investigated in field and growth chamber trials to assess the suitability of willow for phytoremediation. Field uptakes were 2-10 times higher than growth chamber uptakes. Despite high concentrations of cadmium (≥80 mg/kg) and zinc (≥3000 mg/kg) in leaves of willow grown on strongly polluted soil with up to 18 mg Cd/kg, 1400 mg Cu/kg, 500 mg Pb/kg and 3300 mg Zn/kg, it is unsuited on strongly polluted soils because of poor growth. However, willow proved promising on moderately polluted soils (2.5 mg Cd/kg and 400 mg Zn/kg), where it extracted 0.13% of total Cd and 0.29% of the total Zn per year probably representing the most mobile fraction. Cu and Pb are strongly fixed in calcareous soils.     

Release of silver nanoparticles from outdoor facades

In this study we investigate the release of metallic silver nanoparticles (Ag-NP) from paints used for outdoor applications. A facade panel mounted on a model house was exposed to ambient weather conditions over a period of one year. The runoff volume of individual rain events was determined and the silver and titanium concentrations of 36 out of 65 runoff events were measured. Selected samples were prepared for electron microscopic analysis. A strong leaching of the Ag-NP was observed during the initial runoff events with a maximum concentration of 145 μ Ag/l. After a period of one year, more than 30% of the Ag-NP were released to the environment. Particles were mostly <15 nm and are released as composite colloids attached to the organic binders of the paint. Microscopic results indicate that the Ag-NP are likely transformed to considerably less toxic forms such as Ag₂S.     

Determination of four fluoroquinolone antibiotics in tap water in Guangzhou and Macao

Four fluoroquinolone antibiotics (norfloxacin, ciprofloxacin, lomefloxacin, and enrofloxacin) in tap water in Guangzhou and Macao were analyzed using high performance liquid chromatography fluorescence detection. The results showed that all target antibiotics were detected in high rate both in Guangzhou (77.5%) and Macao (100%), ranging from 1.0 to 679.7 ng/L (SD ≤ 37.6) in Guangzhou, and from 2.0 to 37.0 ng/L (SD ≤ 2.5) in Macao. The fluoroquinolone antibiotics pollution in tap water widely distributes in Guangzhou and Macao. In addition, the effect of rainfall on concentration of fluoroquinolone antibiotics in south China was also investigated. Our result indicates that the antibiotic concentration in tap water in Guangzhou tends to obviously reduce at the beginning of rainy season, even decreases below the limit of quantification immediately. Thus, it was clarified that the heavy rain in south China has the function of reducing the fluoroquinolone antibiotics concentrations in tap water.     

Effect of municipal waste water effluent upon the expression of Glutathione S-transferase isoenzymes of brine shrimp Artemia

Multiple isoenzymes of the detoxification enzyme family Glutathione S-transferase are expressed in the brine shrimp Artemia. The number of the major ones detected in crude extract by means of chromatofocusing varied between three and four, depending on the age. Two isoenzymes, one alkaline and one neutral (with corresponding isoelectric points of 8.5 and 7.2) appear to be dominant in all three developmental stages studied, (24, 48, and 72 h after hatching). Culturing Artemia for 48 h after hatching, in artificial sea water prepared by municipal wastewater effluent resulted to significant alterations of the isoenzyme profile. In comparison to organisms cultured for the same period of time in artificial sea water prepared by filtered tap water, the expression of the alkaline isoenzyme decreased by 62% while that of the neutral isoenzyme increased by 58%. Furthermore, the enzyme activity of the major isoenzyme of the acidic area increased by more than two folds. It is worth mentioning that although the specific activity of the total enzyme in the whole body homogenate was elevated, no statistically significant alteration of the Km value was observed. These findings suggest that study of the isoenzyme profile of Glutathione S-transferase may offer high sensitivity in detecting environmental pollution and needs to be further investigated.     

Uranium in Kosovo’s drinking water

The results of this paper are an initiation to capture the drinking water and/or groundwater elemental situation in the youngest European country, Kosovo. We aim to present a clear picture of the natural uranium concentration in drinking water and/or groundwater as it is distributed to the population of Kosovo. Nine hundred and fifty-one (951) drinking water samples were analyzed by inductively coupled plasma mass spectrometry (ICPMS). The results are the first countrywide interpretation of the uranium concentration in drinking water and/or groundwater, directly following the Kosovo war of 1999. More than 98% of the samples had uranium concentrations above 0.01 μg L⁻¹, which was also our limit of quantification. Concentrations up to 166 μg L⁻¹ were found with a mean of 5 μg L⁻¹ and median 1.6 μg L⁻¹ were found. Two point six percent (2.6%) of the analyzed samples exceeded the World Health Organization maximum acceptable concentration of 30 μg L⁻¹, and 44.2% of the samples exceeded the 2 μg L⁻¹ German maximum acceptable concentrations recommended for infant food preparations.     

Sediment quality guidelines for copper and zinc for filter-feeding estuarine oysters?

Sediment quality guidelines (SQGs) assess the ability of bottom sediment to sustain healthy infauna and water quality guidelines (WQGs) provide protection for a designated percentage of aquatic species. Filter-feeding marine species, e.g. oysters and mussels, acquire food from particles in the water column and protection of these animals is not provided by SQGs or WQGs. The current work investigated the relationship between metal (Cu, Zn) concentrations in total and fine-fraction (<62.5 μm) surficial sediment digested in a range of acids and chelating agents and oyster tissue metal concentrations. A strong correlation between oyster tissue Cu and Zn concentrations and fine-fraction surficial sediment digested in 1 M HCl provided a sedimentary guideline which predicted tissue metal concentrations in oysters and established a level (<45 μg g⁻¹ and <1000 μg g⁻¹, respectively) for protecting oysters from exceeding human consumption levels (70 μg g⁻¹ and 1000 μg g⁻¹, respectively).