Quantifying factors related to urban metal contamination in vegetable garden soils of the west and north of Melbourne, Australia.

Vegetable gardens in cities provide communities with fresh vegetables but also may contribute towards public exposure to metals present in soil from historical pollution. Contamination of some Melbourne garden soils with Pb (range 12.9-773 mg kg-1 in soil) was found with some soils exceeding the Australian human health screening criteria for residential land use of 300 mg kg-1. Cadmium concentrations (0.12-1.04 mg kg-1) were above the ambient background soil concentrations of <1 mg kg-1. Nickel concentrations (7.6-40.5 mg kg-1) and Cr (11.6-49.4 mg kg-1) were within the range of expected ambient background concentrations. Distance from the nearest arterial road, house age and the likely use of lead-based paints were the main factors explaining approximately 75% of soil Pb variability in garden soils. Metal concentrations in garden soils of wooden houses were found to be significantly higher than the garden soil of brick and concrete houses (Pb (p < 0.0001)) and Cd (p < 0.001)). Significant correlations were found between backyard garden soil metal concentration and house age for Pb (R2 = 0.83, p < 0.0001) and Cd (R2 = 0.40, p < 0.0002) and the distance from arterial roads for Pb (R2 = 0.38, p < 0.002), while Cr and Ni are related to soil characteristics cation exchange capacity, organic matter, and pH. Vegetable garden with elevated Pb and Cd had recognizable risk factors such as older, painted structures on adjacent houses and closer proximity to arterial roads with higher frequency traffic.

Immobilisation of geogenic arsenic and vanadium in iron-rich sediments and iron stone deposits.

Determination of how geogenic arsenic (As) and vanadium (V) is mobilised from naturally-enriched soils and iron (Fe) stones is integral for understanding the potential risk to the environment from changed land use conditions. Thus, the association of As, V and Fe in As-enriched sediments and Fe stones in Tertiary sediments of Melbourne, Australia, was assessed using chemical extraction methods, micro focused X-ray fluorescence and X-ray absorption spectroscopy. We show that the selective association of As with Fe during Fe stone formation has resulted in As enrichment of up to 60 times the concentration of surrounding soils, and 1000 times higher than mean As concentrations in world soils. In both soil and Fe stones, As was distributed with goethite as arsenate and relatively immobile under oxic conditions. The presence of V on the outer edge of the assessed Fe stone provided evidence of differences in historical As and V solubility; that is, As was immobilised by Fe during an earlier stage of Fe stone formation than V.

Environmental and anthropogenic influences on ambient background concentrations of fluoride in soil.

Excess exposure to fluoride causes substantive health burden in humans and livestock globally. However, few studies have assessed the distribution and controls of variability of ambient background concentrations of fluoride in soil. Ambient background concentrations of fluoride in soil were collated for Greater Melbourne, Greater Geelong, Ballarat and Mitchell in Victoria, Australia (n = 1005). Correlation analysis and machine learning techniques were used to identify environmental and anthropogenic influences of fluoride variability in soil. Sub-soils (>0.3 m deep), in some areas overlying siltstone and sandstone, and to a lesser extent, overlying basalt, were naturally enriched with fluoride at concentrations above ecological thresholds for grazing animals. Soil fluoride enrichment was predominantly influenced by parent material (mineralogy), precipitation (illuviation), leaching during palaeoclimates and marine inputs. Industrial air pollution did not significantly influence ambient background concentrations of fluoride at a regional scale. However, agricultural practices (potentially the use of phosphate fertilisers) were indicated to have resulted in added fluoride to surface soils overlying sediments. Geospatial variables alone were not sufficient to accurately model ambient background soil fluoride concentrations. A multiple regression model based on soil chemistry and parent material was shown to accurately predict ambient background fluoride concentrations in soils and support assessment of fluoride enrichment in the environment.

Geochemical indices and regression tree models for estimation of ambient background concentrations of copper, chromium, nickel and zinc in soil.

Geochemical ratios between elements of environmental concern and Fe have been recommended for estimation of "background" concentrations of Cr, Cu, Ni and Zn in soil. However, little research has occurred to assess the consistency of geochemical ratios across soils developed in different environments. Broad application of generic geochemical ratios could result in under or over estimation of anthropogenic impacts to soil and subsequent inaccurate assessment of risk to the environment. A soil survey was undertaken in Victoria, Australia, including collection of samples (n = 622) from surface (0-0.1 m below ground level) and sub-surface (0.3-0.6 m below ground level) soils, overlying Tertiary-Quaternary basalt, Tertiary sediments and Silurian siltstones and sandstones. Samples were analyzed for metals and soil physical and chemical properties (particle size, cation exchange capacity, organic matter and pH). Geochemical correlations between elements in soils from different parent materials and environments were compared against geochemical relationships reported in Australia and internationally. Ratios of Cr and Fe were relatively consistent across parent materials, and comparable to published models for estimation of background Cr. Conversely, ratios between Cu, Ni, and Zn with Fe, were variable between soils developed in different weathering environments and/or soil depths. Alternative regression equations and rule based regression tree models were developed as an improved means for prediction of ambient background Cu, Ni and Zn concentrations in soil. Ambient background concentrations of Ni and Cr were predictable across parent materials and depths, allowing these models to be extended to soils across Australia and potentially internationally.

Evaluation of environmental and anthropogenic influences on ambient background metal and metalloid concentrations in soil.

There has been a global shift in environmental risk assessment towards quantifying ambient background concentrations of metals/metalloids in soil. Whilst bedrock has been shown to be a key driver of metal/metalloid variability in soil, few researchers have assessed controls of ambient background concentrations in soils of similar bedrock. A soil survey was undertaken ofGreater Melbourne, Greater Geelong, Ballarat and Mitchell in Victoria, Australia for elements of potential environmental concern: As, Cd, Cr, Cu, Ni, Hg, Pb and Zn. Samples (n=622) were collected from surface (0 to 0.1m) and sub-surface (0.3 to 0.6m) soils, overlying Tertiary-Quaternary basalt, Tertiary sediments and Silurian siltstone and sandstone. In addition, background soil data from open-source environmental assessment reports (n=5512) were collated to support the understanding of natural enrichment, particularly at depths >0.6m. Factor analysis, supported by correlation analysis and auxiliary geo-spatial data, provided an improved understanding of where and how background metal/metalloid enrichment occurs in the environment. Weathering during paleoclimates was the predominant influence of background metal/metalloid variability in soils overlying similar bedrock. Other key influences of metal/metalloid variability in soil included hydraulic leaching of alkali elements, biological cycling, topography and alluvial transfer of silt and sand from mineralised regions. In addition, urbanisation positively correlated with Pb and Zn concentrations in surface soils suggesting that anthropogenic activities may have resulted in diffuse Pb and Zn contamination of urban soil.

Evaluation of methods for managing censored results when calculating the geometric mean.

Currently, there are conflicting views on the best statistical methods for managing censored environmental data. The method commonly applied by environmental science researchers and professionals is to substitute half the limit of reporting for derivation of summary statistics. This approach has been criticised by some researchers, raising questions around the interpretation of historical scientific data. This study evaluated four complete soil datasets, at three levels of simulated censorship, to test the accuracy of a range of censored data management methods for calculation of the geometric mean. The methods assessed included removal of censored results, substitution of a fixed value (near zero, half the limit of reporting and the limit of reporting), substitution by nearest neighbour imputation, maximum likelihood estimation, regression on order substitution and Kaplan-Meier/survival analysis. This is the first time such a comprehensive range of censored data management methods have been applied to assess the accuracy of calculation of the geometric mean. The results of this study show that, for describing the geometric mean, the simple method of substitution of half the limit of reporting is comparable or more accurate than alternative censored data management methods, including nearest neighbour imputation methods.

Assessment of ambient background concentrations of elements in soil using combined survey and open-source data.

Understanding ambient background concentrations in soil, at a local scale, is an essential part of environmental risk assessment. Where high resolution geochemical soil surveys have not been undertaken, soil data from alternative sources, such as environmental site assessment reports, can be used to support an understanding of ambient background conditions. Concentrations of metals/metalloids (As, Mn, Ni, Pb and Zn) were extracted from open-source environmental site assessment reports, for soils derived from the Newer Volcanics basalt, of Melbourne, Victoria, Australia. A manual screening method was applied to remove samples that were indicated to be contaminated by point sources and hence not representative of ambient background conditions. The manual screening approach was validated by comparison to data from a targeted background soil survey. Statistical methods for exclusion of contaminated samples from background soil datasets were compared to the manual screening method. The statistical methods tested included the Median plus Two Median Absolute Deviations, the upper whisker of a normal and log transformed Tukey boxplot, the point of inflection on a cumulative frequency plot and the 95th percentile. We have demonstrated that where anomalous sample results cannot be screened using site information, the Median plus Two Median Absolute Deviations is a conservative method for derivation of ambient background upper concentration limits (i.e. expected maximums). The upper whisker of a boxplot and the point of inflection on a cumulative frequency plot, were also considered adequate methods for deriving ambient background upper concentration limits, where the percentage of contaminated samples is <25%. Median ambient background concentrations of metals/metalloids in the Newer Volcanic soils of Melbourne were comparable to ambient background concentrations in Europe and the United States, except for Ni, which was naturally enriched in the basalt-derived soils of Melbourne.