Role of solids in heavy metals build-up on urban road surfaces

Solids are widely identified as a carrier of harmful pollutants in stormwater runoff exerting a significant risk to receiving waters. This paper outlines the findings of an in-depth investigation on heavy metal adsorption to solids surfaces. Pollutant build-up samples collected from sixteen road sites in residential, industrial and commercial land uses were separated into four particle size ranges and analysed for a range of physico-chemical parameters and nine heavy metals including Iron (Fe), Aluminum (Al), Lead (Pb), Zinc (Zn), Cadmium (Cd), Chromium (Cr), Manganese (Mn), Nickel (Ni) and Copper (Cu). High specific surface area (SSA) and total organic carbon (TOC) content in finer particle size ranges was noted, thus confirming strong correlations with heavy metals. Based on their physico-chemical characteristics, two different types of solids originating from traffic and soil sources were identified. Solids generated by traffic were associated with high loads of heavy metals such as Cd and Cr with strong correlation with SSA. This suggested the existence of surface dependent bonds such as cation exchange between heavy metals and solids. In contrast, Fe, Al and Mn which can be attributed to soil inputs showed strong correlation with TOC suggesting strong bonds such as chemsorption. Zn was found to be primarily attached to solids by bonding with the oxides of Fe, Al and Mn. The data analysis also confirmed the predominance of the finer fraction, with 70% of the solids being finer than 150 µm and containing 60% of the heavy metal pollutant load.

Liquid metal marbles

Liquid metal marbles that are droplets of liquid metal encapsulated by micro- or nanoparticles are introduced. Droplets of galinstan liquid metal are coated with insulators (including Teflon and silica) and semiconductors (including WO3, TiO2, MoO3, In2O3 and carbon nanotubes) by rolling over a powder bed and also by submerging in colloidal suspensions. It is shown that these marbles can be split and merged, can be suspended on water, and are even stable when moving under the force of gravity and impacting a flat solid surface. Furthermore, the marble coating can operate as an active electronic junction and the nanomaterial coated liquid metal marble can act as a highly sensitive electrochemical based heavy metal ion sensor. This new element thus represents a significant platform for the advancement of research into soft electronics.

Enrichment, distribution and sources of heavy metals in the sediments of Deception Bay, Queensland, Australia

Sediment samples from 13 sampling sites in Deception Bay, Australia were analysed for the presence of heavy metals. Enrichment factors, modified contamination indices and Nemerow pollution indices were calculated for each sampling site to determine sediment quality. The results indicate significant pollution of most sites by lead (average enrichment factor (EF) of 13), but there is also enrichment of arsenic (average EF 2.3), zinc (average EF 2.7) and other heavy metals. The modified degree of contamination indices (average 1.0) suggests that there is little contamination. By contrast, the Nemerow pollution index (average 5.8) suggests that Deception Bay is heavily contaminated. Cluster analysis was undertaken to identify groups of elements. Strong correlation between some elements and two distinct clusters of sampling sites based on sediment type was evident. These results have implications for pollution in complex marine environments where there is significant influx of sand and sediment into an estuarine environment.

Gold nanospikes based microsensor as a highly accurate mercury emission monitoring system

Anthropogenic elemental mercury (Hg0) emission is a serious worldwide environmental problem due to the extreme toxicity of the heavy metal to humans, plants and wildlife. Development of an accurate and cheap microsensor based online monitoring system which can be integrated as part of Hg0 removal and control processes in industry is still a major challenge. Here, we demonstrate that forming Au nanospike structures directly onto the electrodes of a quartz crystal microbalance (QCM) using a novel electrochemical route results in a self-regenerating, highly robust, stable, sensitive and selective Hg0 vapor sensor. The data from a 127 day continuous test performed in the presence of volatile organic compounds and high humidity levels, showed that the sensor with an electrodeposted sensitive layer had 260% higher response magnitude, 3.4 times lower detection limit (,22 mg/m3 or ,2.46 ppbv) and higher accuracy (98% Vs 35%) over a Au control based QCM (unmodified) when exposed to a Hg0 vapor concentration of 10.55 mg/m3 at 1016C. Statistical analysis of the long term data showed that the nano-engineered Hg0 sorption sites on the developed Au nanospikes sensitive layer play a critical role in the enhanced sensitivity and selectivity of the developed sensor towards Hg0 vapor.

Temporal trends and bioavailability assessment of heavy metals in the sediments of Deception Bay, Queensland, Australia

Thirteen sites in Deception Bay, Queensland, Australia were sampled three times over a period of 7 months and assessed for contamination by a range of heavy metals, primarily As, Cd, Cr, Cu, Pb and Hg. Fraction analysis, enrichment factors and Principal Components Analysis-Absolute Principal Component Scores (PCA-APCS) analysis were conducted in order to identify the potential bioavailability of these elements of concern and their sources. Hg and Te were identified as the elements of highest enrichment in Deception Bay while marine sediments, shipping and antifouling agents were identified as the sources of the Weak acid Extractable Metals (WE-M), with antifouling agents showing long residence time for mercury contamination. This has significant implications for the future of monitoring and regulation of heavy metal contamination within Deception Bay.

Development of a hybrid pollution index for heavy metals in marine and estuarine sediments

Heavy metal pollution of sediments is a growing concern in most parts of the world, and numerous studies focussed on identifying contaminated sediments by using a range of digestion methods and pollution indices to estimate sediment contamination have been described in the literature. The current work provides a critical review of the more commonly used sediment digestion methods and identifies that weak acid digestion is more likely to provide guidance on elements that are likely to be bioavailable than other traditional methods of digestion. This work also reviews common pollution indices and identifies the Nemerow Pollution Index as the most appropriate method for establishing overall sediment quality. Consequently, a modified Pollution Index that can lead to a more reliable understanding of whole sediment quality is proposed. This modified pollution index is then tested against a number of existing studies and demonstrated to give a reliable and rapid estimate of sediment contamination and quality.

Heavy metals in the sediments of Northern Moreton Bay, Queensland, Australia

This project was the first comprehensive assessment of heavy metals to be conducted in the sediments of Northern Moreton Bay since the 1970s and found that shipping and shipping related activities contributed significantly to the level of sediment contamination in the area. The study was also used to develop and test new methods of assessing heavy metal sediment quality.

Studies on metal complex formation of environmentally friendly aminopolycarboxylate chelating agents

Aminopolykarboksyylaatteja, kuten etyleenidiamiinitetraetikkahappoa (EDTA), on käytetty useiden vuosikymmenien ajan erinomaisen metalli-ionien sitomiskyvyn vuoksi kelatointiaineena lukuisissa sovelluksissa sekä analytiikassa että monilla teollisisuuden aloilla. Näiden yhdisteiden biohajoamattomuus on kuitenkin herättänyt huolta viime aikoina, sillä niiden on havaittu olevan hyvin pysyviä luonnossa. Tämä työ on osa laajempaa tutkimushanketta, jossa on tavoitteena löytää korvaavia kelatointiaineita EDTA:lle. Tutkimuksen aiheena on kuuden kelatointiaineen metalli-ionien sitomiskyvyn kartoitus. EDTA:a paremmin luonnossa hajoavina nämä ovat ympäristöystävällisiä ehdokkaita korvaaviksi kelatointiaineiksi useisiin sovelluksiin. Työssä tutkittiin niiden kompleksinmuodostusta useiden metalli-ionien kanssa potentiometrisella titrauksella. Metalli-ionivalikoima vaihteli hieman kelatointiaineesta riippuen sisältäen magnesium-, kalsium-, mangaani-, rauta-, kupari-, sinkki-, kadmium-, elohopea-, lyijy- ja lantaani-ionit. Tutkittavat metallit oli valittu tähtäimessä olevien sovellusten, synteesissä ilmenneiden ongelmien tai ympäristönäkökohtien perusteella. Tulokset osoittavat näiden yhdisteiden metallinsitomiskyvyn olevan jonkin verran heikompi kuin EDTA:lla, mutta kuitenkin riittävän useisiin sovelluksiin kuten sellunvalkaisuprosessiin. Myrkyllisten raskasmetallien, kadmiumin, elohopen ja lyijyn kohdalla EDTA:a heikompi sitoutuminen on eduksikin, koska se yhdistettynä parempaan biohajoavuuteen saattaa alentaa tutkittujen yhdisteiden kykyä mobilisoida kyseisiä metalleja sedimenteistä. Useimmilla tutkituista yhdisteistä on ympäristönäkökulmasta etuna myös EDTA:a pienempi typpipitoisuus.

Human health risk assessment of heavy metals in urban stormwater

Toxic chemical pollutants such as heavy metals (HMs) are commonly present in urban stormwater. These pollutants can pose a significant risk to human health and hence a significant barrier for urban stormwater reuse. The primary aim of this study was to develop an approach for quantitatively assessing the risk to human health due to the presence of HMs in stormwater. This approach will lead to informed decision making in relation to risk management of urban stormwater reuse, enabling efficient implementation of appropriate treatment strategies. In this study, risks to human health from heavy metals were assessed as hazard index (HI) and quantified as a function of traffic and land use related parameters. Traffic and land use are the primary factors influencing heavy metal loads in the urban environment. The risks posed by heavy metals associated with total solids and fine solids (<150µm) were considered to represent the maximum and minimum risk levels, respectively. The study outcomes confirmed that Cr, Mn and Pb pose the highest risks, although these elements are generally present in low concentrations. The study also found that even though the presence of a single heavy metal does not pose a significant risk, the presence of multiple heavy metals could be detrimental to human health. These findings suggest that stormwater guidelines should consider the combined risk from multiple heavy metals rather than the threshold concentration of an individual species. Furthermore, it was found that risk to human health from heavy metals in stormwater is significantly influenced by traffic volume and the risk associated with stormwater from industrial areas is generally higher than that from commercial and residential areas.

Comparison of partial extraction reagents for assessing potential bioavailability of heavy metals in sediments

Assessment of heavy metal bioavailability in sediments is complex because of the number of partial extraction methods available for the assessment and the general lack of certified reference materials. This study evaluates five different extraction methodologies to ascertain the relative strengths and weaknesses of each method. The results are then compared to previously published work to ascertain the most effective partial extraction technique, which was established to be dilute (0.75 – 1 M) nitric acid solutions. These results imply that single reagent; weak acid extractions provide a better assessment of potentially bioavailable metals than the chelating agents used in sequential extraction methods.

Impact of heavy metals on bacterial communities from mangrove soils of the Mahanadi Delta (India)

This study aimed to assess soil nutrient status and heavy metal content and their impact on the predominant soil bacterial communities of mangroves of the Mahanadi Delta. Mangrove soil of the Mahanadi Delta is slightly acidic and the levels of soil nutrients such as carbon, nitrogen, phosphorous and potash vary with season and site. The seasonal average concentrations (g/g) of various heavy metals were in the range: 14810-63370 (Fe), 2.8-32.6 (Cu), 13.4-55.7 (Ni), 1.8-7.9 (Cd), 16.6-54.7 (Pb), 24.4-132.5 (Zn) and 13.3-48.2 (Co). Among the different heavy metals analysed, Co, Cu and Cd were above their permissible limits, as prescribed by Indian Standards (Co=17g/g, Cu=30 g/g, Cd=3-6 g/g), indicating pollution in the mangrove soil. A viable plate count revealed the presence of different groups of bacteria in the mangrove soil, i.e. heterotrophs, free-living N-2 fixers, nitrifyers, denitrifyers, phosphate solubilisers, cellulose degraders and sulfur oxidisers. Principal component analysis performed using multivariate statistical methods showed a positive relationship between soil nutrients and microbial load. Whereas metal content such as Cu, Co and Ni showed a negative impact on some of the studied soil bacteria.

Processo de separação por membranas para remoção de sulfato de níquel e zinco de efluente sintético de indústrias metal-mecânicas

O objetivo do presente trabalho foi investigar o desempenho de membranas comerciais e funcionalizadas na remoção de metais pesados de efluentes sintéticos, simulando os efluentes gerados pelas indústrias metal-mecânicas. As membranas funcionalizadas foram preparadas em laboratório a partir de diferentes poli (éter imidas) sulfonadas, SPEI, que apresentavam alta hidrofilicidade e capacidade de troca iônica. As permeabilidades hidráulicas das membranas de SPEI aumentaram com o grau de sulfonação. Porém, as rejeições foram ainda muito baixas comparadas as membranas comerciais. Por esta razão, algumas membranas comerciais (NF-90, SW30, HRP98PP e BW30LE) foram investigadas e avaliadas quanto ao comportamento da permeabilidade de água e o grau de rejeição a metais pesados. Os resultados mostraram que a membrana de osmose inversa de baixa energia (BW30LE) tinha o melhor fluxo de água (48,44 L/h.m2) e grau de rejeição a cádmio (98%). Logo, ela foi selecionada para o tratamento dos efluentes sintéticos de indústrias metal-mecânicas contendo níquel e zinco. As indústrias da região de Valencia, na Espanha, forneceram amostras de seus efluentes para análise quantitativa, possibilitando o prepararo de soluções sintéticas modelos. Os resultados foram obtidos variando algumas condições de permeação, tais como a força motriz, o pH e a concentração dos metais na solução de alimentação. Os resultados indicaram que o processo de osmose inversa com a membrana BW30LE é altamente adequado para o tratamento de efluentes contendo metais pesados

Accumulation of Heavy Metals in Franciscanas from Buenos Aires Province, Argentina

Marine mammals accumulate heavy metals in their tissues at different concentrations according to trophic levels and environmental conditions. The franciscana (Pontoporia blainvillei) is a small coastal species inhabiting the marine and estuarine areas of the Southwestern Atlantic Ocean. Its diet includes numerous species of small fish, squid and crustaceans. The aims of this study were to (i) assess the heavy metal concentration and burden distribution in different franciscana age classes and sex, and to (ii) evaluate both the accumulation processes and the transplacental transference of zinc, cadmium, copper and total mercury. Heavy metal concentrations (wet weight) were determined in eighteen dolphins by Atomic Absorption Spectrophotometry (AAS), by the cold vapour technique (mercury) or with air/acetylene flame (cadmium, zinc and copper). Liver showed the highest concentrations of mercury (max. 8.8 mg/g), zinc (max. 29.7 mg/g) and copper (max. 19.0 mg/g), whereas the highest cadmium concentrations (max. 6.7 mg/g) were found in kidney. Adults contained the highest concentrations for all heavy metals, followed by juveniles and calves in decreasing order, suggesting an age-related accumulation. No differences (p<0.05) were found between sexes within each age class. Organ burden distribution followed the same pattern for all metals and age classes: liver tissues contained maximum burdens. Mercury concentrations were higher than those of cadmium in both foetuses and newborns; and neither metal could be detected in the foetus. The analysed data suggested differences in the placental transference between metals, being significant for mercury and almost null in the case of cadmium. We can conclude that franciscana accumulates heavy metals and, due to its coastal distribution, it may be considered as a biomonitor of its environment. SPANISH: Los mamíferos marinos acumulan metales pesados en sus tejidos cuyas concentraciones están en relación con su nivel trófico y las condiciones ambientales. La franciscana (Pontoporia blainvillei) es una especie costera que habita áreas marinas y estuariales en el Atlántico Sudoccidental. Su dieta está constituída por peces, como item alimentario principal, calamares y crustáceos. El objetivo del presente trabajo es estudiar la distribución de metales pesados en diferentes clases de edad y en ambos sexos, evaluando procesos de acumulación y cargas de cadmio, mercurio total, cinc y cobre. Las concentraciones de metales pesados (en peso húmedo) fueron determinadas en dieciocho delfines por Espectrofotometría de Absorción Atómica (EAA), usando la técnica de vapor frío (mercurio) o llama de aire/acetileno (cadmio, cinc y cobre). El hígado presentó las concentraciones más altas de mercurio (máx. 8,8 mg/g), cinc (máx. 29,7 mg/g) y cobre (máx. 19,0 mg/g), mientras que las más altas de cadmio (máx. 6,7 mg/g) fueron encontradas en el riñón. Los adultos presentaron los niveles más altos, presentando los juveniles y cachorros concentraciones menores, lo cual sugirió una acumulación con la edad. No se encontraron diferencias significativas (p < 0,05) entre sexos dentro de cada clase de edad. Las cargas de metales pesados en los órganos presentaron la misma disribución para todos los metales y clases de edad. Los valores más altos fueron encontrados en el hígado, incluyendo los correspondientes a cadmio. Las concentraciones de mercurio y cadmio fueron no detectables en el feto, mientras que las de mercurio fueron superiores a las de cadmio en los cachorros. Los datos encontrados en el feto sugieren una transferencia nula a través de la placenta. Podemos concluir que P.blainvillei acumula metales pesados en sus tejidos y debido a su distribución costera, esta especie puede ser considerada como un biomonitor de su ambiente.

The history of contamination in sediments from the Mersey Estuary. Development of a chronology for the contamination of the Mersey Estuary by heavy metals and organochlorines

This is the history of contamination in sediments from the Mersey Estuary: Development of a chronology for the contamination of the Mersey Estuary by heavy metals and organochlorines Report produced by the Environment Agency in 1998. This report looks at the history of industrial contamination of the Mersey and Ribble Estuaries back to the early part of the last century, many decades before the start of monitoring programmes providing a remarkably detailed picture of very complex changes. There is a clear record in the sediment of the contamination by each heavy metal (including: Cu, Cr, Hg, Pb, Zn) and organochlorine chemical (including DDT isomers and PCB congeners) studied. The results of the study clearly show the increases in levels of contamination as industry expanded early last century followed by various improvements as this century progressed. Each pollutant has its own idiosyncratic pattern of change with some improvements predating modern environmental concerns whilst other changes seem to relate directly to recent improvements in legislative control. Overall, for the pollutants studied, the results clearly demonstrate the magnitude of improvement that has been achieved in what was a very polluted area. The only major reservation to this story is that despite the wide range of substances covered, many other potentially important pollutants remain to be studied in a similar manner.

Concentration and distribution of heavy metals (lead, cadmium, chromium, copper, nickel, zinc) in Karachi shore and offshore sediments

A study to measure the heavy metal pollution level in the sediment of coastal and offshore area indicates that high concentration of heavy metals were found around Manora channel and eastern coast of Karachi. In comparison with coastal areas, relatively low concentration of heavy metals was recorded in the offshore area. The result shows that sewage and industrial wastes are the main source of heavy metal pollution in the coastal area. The concentration of heavy metals in the sediments is as follows: Chromium 10.4-33.69, nickel 13.3-47.6, lead 10.0-39.04, cadmium 0.08-0.21, zinc 7.4-73.2 and copper 9.44-18.56 mg/kg. In the offshore areas strong correlation was observed between copper and organic carbon, and calcium carbonate and cadmium. In the shore area such correlation has been recorded among nickel, chromium, zinc, and chromium and copper. The Karachi. coast is viewed as moderately polluted when compared to other continental coastal areas.