Long-term use of galvanized steel in external applications. Aspects of patina formation, zinc runoff, barrier properties of surface treatments, and coatings and environmental fate

Galvanized steel structures are used in a large variety of external constructions in the modern urban society, and their beneficial properties from a corrosion and oxidation perspective are well known. Less investigated is the extent of their contribution to the diffuse dispersion of zinc in the society and also to the environmental fate of corrosion-induced released zinc. This paper presents long-term runoff rates of zinc from galvanized steel surfaces with main focus on hot-dipped galvanized steel exposed for up to 10 years at nonsheltered urban atmospheric conditions. The long-term capacities of a naturally formed patina and the presence of surface treatments and coatings to hinder and reduce corrosion-induced zinc runoff from galvanized steel are elucidated. The environmental interaction of zinc runoff and concrete surfaces in pavement and urban storm drain systems is highlighted and the high capacity of concrete to retain released zinc presented.     

Risks of using membrane filtration for trace metal analysis and assessing the dissolved metal fraction of aqueous media--a study on zinc, copper and nickel

Membrane filtration is commonly performed for solid-liquid separation of aqueous solutions prior to trace metal analysis and when assessing “dissolved” metal fractions. Potential artifacts induced by filtration such as contamination and/or adsorption of metals within the membrane have been investigated for different membrane materials, metals, applied pressures and pre-cleaning steps. Measurements have been conducted on aqueous solutions including well-defined metal standards, ultrapure water, and on runoff water from corroded samples.Filtration using both non-cleaned and pre-cleaned filters revealed contamination and adsorption effects, in particular pronounced for zinc, evident for copper but non-significant for nickel. The results clearly show these artifacts to be non-systematic both for non-cleaned and pre-cleaned membranes. The applied pressure was of minor importance.Measurements of the labile fraction by means of stripping voltammetry clearly elucidate that membrane filtration followed by total metal analysis cannot accurately assess the labile or the dissolved metal fraction.     

A Comparison Between Corrosion Rates and Runoff Rates from New and Aged Copper and Zinc as Roofing Material

Recently there has been anincreased environmental concern in severalcountries in Europe, in particular in Sweden andin the Netherlands regarding the amount of copperand zinc that is released from building materialsinto society. Due to lack of runoff data, thelegislators have so far used corrosion ratesmeasured during the last 20 years to calculatequantities of metal released from buildingsassuming that the quantity of metal corrosionequals the quantity of metal runoff. Withdecreasing levels of environmental pollutantsduring the last decade in Europe, it is importantto determine more recent and hence morerepresentative corrosion and runoff rates to beused in the calculations. For this reason a field exposure program was implemented during 48 weeks in an urbanatmosphere in Sweden determining corrosion andrunoff rates for copper and zinc of differentage. New copper exposed for 48 weeks in the urbanatmosphere shows a corrosion rate of 6.7gm^-2y^-1 and an almost constant runoff rate of1.3 gm^-2y^-1 during the period. Therunoff rate is significantly lower than thecorrosion rate and represents only a fraction(20%) of the total amount of corroded metalduring this period. Zinc shows a graduallydecreasing corrosion rate with time being 5.0gm^-2y^-1 after 48 weeks of exposure. Therunoff rate is relatively stable with an averagerate of 3.1 gm^-2y^-1 during the sameperiod. This value represents 60% of the totalamount of corroded zinc. The effect of panel age has been investigatedin parallel field and laboratory studies. Theresults show that naturally aged copper exhibitssomewhat higher average runoff rates (2 gm^-2y^-1) than new copper, probably due to acombined effect of storage and weatherconditions. No significant difference in runoffrate can be found between new and naturally agedzinc. The field and laboratory investigationsshow that precipitation rate and amount influence the magnitude of the runoff rate forboth copper and zinc.     

Corrosion-induced release of Cu and Zn into rainwater from brass, bronze and their pure metals. A 2-year field study

A 2-year field study has been conducted in an urban environment to provide annual release rates of copper and zinc from brass (20 wt% Zn) and copper and tin from bronze (6 wt% Sn) compared to sheets of their pure alloy constituents, copper and zinc. Despite relatively low nominal bulk alloy content, substantially more zinc was released from brass compared to copper. Both metals were released at a significantly slower rate from the brass alloy, compared to the pure metals. The proportion of release rates of copper and zinc from the alloy differed significantly from their proportions in the bulk alloy. Bronze showed relatively constant release rates of copper, being similar to that of pure copper sheet. The release of tin from bronze was negligible. The results clearly show that alloys and the pure metals behave very differently when exposed to rainwater. Accordingly, release rates from pure metals cannot be used to predict release rates of individual constituents from their alloys. Generated data are of importance within REACH, the new chemical policy of the European commission, where metal alloys erroneously are being treated as mixtures of chemical substances.     

Corrosion-induced release of the main alloying constituents of manganese-chromium stainless steels in different media

The main focus of this paper is the assessment of release rates of chromium, nickel, iron and manganese from manganese-chromium stainless steel grades of low nickel content. The manganese content varied between 9.7 and 1.5 wt% and the corresponding nickel content between 1 and 5 wt%. All grades were exposed to artificial rain and two were immersed in a synthetic body fluid of similar pH but of different composition and exposure conditions. Surface compositional studies were performed using X-ray photoelectron spectroscopy (XPS) in parallel to correlate the metal release process with changes in surface oxide properties. All grades, independent of media, revealed a time-dependent metal release process with a preferential low release of iron and manganese compared to nickel and chromium while the chromium content of the surface oxide increased slightly. Manganese was detected in the surface oxide of all grades, except the grade of the lowest manganese bulk content. No nickel was observed in the outermost surface oxide. Stainless steel grades of the lowest chromium content (approximately 16 wt%) and highest manganese content (approximately 7-9 wt%), released the highest quantity of alloy constituents in total, and vice versa. No correlation was observed between the release rate of manganese and the alloy composition. Released main alloy constituents were neither proportional to the bulk alloy composition nor to the surface oxide composition.     

Bioavailability of zinc in runoff water from roofing materials

Corrosion and runoff from zinc-coated materials and outdoor structures is an important source for the dispersion of zinc in the environment. Being part of a large inter-disciplinary research project, this study presents the bioavailability of zinc in runoff water immediately after release from the surface of 15 different commercially available zinc-based materials exposed to the urban environment of Stockholm, Sweden. Runoff water was analysed chemically and evaluated for its possible environmental impact, using both a biosensor test with the bacteria Alcaligenes eutrophus (Biomet^®) and the conventional 72 h growth inhibition test with the green alga Raphidocelis subcapitata. Chemical speciation modelling revealed that most zinc (94.3–99.9%) was present as the free Zn ion, the most bioavailable speciation form. These findings were confirmed by the results of the biosensor test (Biomet^®) which indicated that all zinc was indeed bioavailable. Analysis of the ecotoxicity data also suggested that the observed toxic effects were due to the presence of Zn²⁺ ions. Finally, regression analysis showed that, for this type of runoff samples, the rapid screening biosensor was capable of predicting (a) the total amount of zinc present in the runoff samples (R² of 0.93–0.98; p<0.05) and (b) the observed 72 h-EbC₅₀s (R² of 0.69–0.97; p<0.05).     

Metal release from stainless steel particles in vitro-influence of particle size

Human inhalation of airborne metallic particles is important for health risk assessment. To study interactions between metallic particles and the human body, metal release measurements of stainless steel powder particles were performed in two synthetic biological media simulating lung-like environments. Particle size and media strongly influence the metal release process. The release rate of Fe is enhanced compared with Cr and Ni. In artificial lysosomal fluid (ALF, pH 4.5), the accumulated amounts of released metal per particle loading increase drastically with decreasing particle size. The release rate of Fe per unit surface area increases with decreasing particle size. Compared with massive sheet metal, fine powder particles (<4 microm) show similar release rates of Cr and Ni, but a higher release rate of Fe. Release rates in Gamble's solution (pH 7.4), for all powders investigated, are significantly lower compared to ALF. No clear trend is seen related to particle size in Gamble's solution.     

Metal release rate from AISI 316L stainless steel and pure Fe, Cr and Ni into a synthetic biological medium--a comparison

Metal release rates from stainless steel grade 316L were investigated in artificial lysosomal fluid (ALF), simulating a human inflammatory cell response. The main focus was placed on release rates of main alloying elements using graphite furnace atomic absorption spectroscopy, and changes in surface oxide composition by means of X-ray photoelectron spectroscopy. To emphasise that alloys and pure metals possess totally different intrinsic properties, comparative studies were performed on the pure alloying constituents: iron, nickel and chromium. Significant differences in release rates were observed due to the presence of a passive surface film on stainless steel. Iron and nickel were released at rates more than 300 times lower from the 316L alloy compared with the pure metals whereas the release rate of chromium was similar. Iron was preferentially released compared with nickel and chromium. Immersion in ALF resulted in the gradual enrichment of chromium in the surface film, a small increase of nickel, and the reduction of oxidized iron with decreasing release rates of alloy constituents as a result. As expected, released metals from stainless steel grade 316L were neither in proportion to the bulk alloy composition nor to the surface film composition.     

Modelling and mapping of copper runoff for Europe

A predictive runoff rate model for copper has been refined and used to generate copper runoff maps for Europe. The new model is based on laboratory and field runoff data and expresses the runoff rate R (g m(-2) yr(-1)) through two contributions, both with a physical meaning: R = (0.37SO(0.5)(2) = 0.96 rain10(-0.62 pH) (cos(theta)/cos(45 degree)). Input parameters are the SO(2) concentration (microg m(-3)), pH, amount of rain (mm yr(-1)), and surface angle of inclination (theta). The first contribution originates from dry periods between rain events (the first-flush effect) and the second from the rain events. The dry term has been refined in comparison to the original model by assuming a mass balance between measured corrosion mass loss, calculated copper retention in the patina and predicted copper runoff. The refined model predicts 76% of all reported runoff rates, worldwide, within 35% from their measured value. This includes sites with low SO(2) concentration, where the original model erroneously predicted higher runoff rates than corrosion rates. Based on environmental data from the EMEP programme for the years 1980-2000, the new model has been used to derive runoff rate maps for Europe with 50 x 50 km grid resolution. The runoff mapping shows a substantial reduction in runoff rate over the investigated time period, and with copper runoff rates now generally less than 2 g m(-2) yr(-1).     

Runoff rates,chemical speciation and bioavailability of copper released from naturally patinated copper

The release of copper, induced by atmospheric corrosion, from naturally patinated copper of varying age (0 and 30 years) has been investigated together with its potential ecotoxic effect. Results were generated in an interdisciplinary research effort in which corrosion science and ecotoxicology aspects were combined. The aim of the investigation was to elucidate the situation when copper-containing rainwater leaves a roof in terms of runoff rate, chemical speciation, bioavailability and ecotoxicity effects. Data have been collected during a three-year field exposure conducted in the urban environment of Stockholm, Sweden. The potential environmental effects have been evaluated using a combination of a copper specific biosensor test with the bacterium Alcaligenes eutrophus and the conventional 72-h growth inhibition test with the green alga Raphidocelis subcapitata. The results show annual runoff rates between 1.0 and 1.5 g/m2 year for naturally patinated copper of varying age. The runoff rate increased slightly with patina age, which mainly is attributed to the enhanced first flush effect observed on thicker patina layers. The total copper concentration in investigated runoff samplings ranged from 0.9 to 9.7 mg/l. Both computer modeling and experimental studies revealed that the majority (60-100%) of released copper was present as the free hydrated cupric ion, Cu(H2O)6(2+), the most bioavailable copper species. However, other copper species in the runoff water, such as, e.g. Cu(OH)+ and Cu2(OH)2(2+), were also bioavailable. The copper-containing runoff water, sampled directly after release from the roof, caused significant reduction in growth rate of the green alga. It should be emphasized that the results describe the runoff situation immediately after release from the copper roof and not the real environmental ecotoxicity. Therefore the data should only be used as an initial assessment of the potential environmental effect of copper runoff from building applications. Future risk assessments should also consider dilution effects of copper, changes in its chemical speciation and bioavailability during environmental entry, and type and sensitivity of the receiving ecosystem.