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Plant residues as direct and indirect sources of hydrocarbons in soils: current issues and legal implications. Marco Vecchiato, Tiziano Bonato, Andrea Bertin, Elena Argiriadis, Carlo Barbante, and Rossano Piazza Environ. Sci. Technol. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.estlett.7b00464 • Publication Date (Web): 10 Nov 2017 Downloaded from http://pubs.acs.org on November 13, 2017
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Plant Residues as Direct and Indirect Sources of Hydrocarbons in Soils:
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Current Issues and Legal Implications.
3 4 5 6
Marco Vecchiato a*, Tiziano Bonato Rossano Piazza
a,c
a,b
, Andrea Bertin b, Elena Argiriadis a, Carlo Barbante
a,c
,
.
7 8 9 10
a
Department of Environmental Sciences, Informatics and Statistics (DAIS), Ca’ Foscari University of
Venice, Via Torino 155, 30172 Venezia-Mestre, Venice, Italy.
11 12
b
Società Estense Servizi Ambientali (S.E.S.A. S.p.A.), Via Comuna 5/B, 35042, Este, PD, Italy.
13 14
c
15
Venezia-Mestre, Venice, Italy.
Institute for the Dynamics of Environmental Processes (IDPA-CNR), Via Torino 155, 30172
16 17 18 19
*Corresponding author: Marco Vecchiato
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e-mail:
[email protected] 21
phone: +39 0412348545
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Keywords: Soil; Total petroleum hydrocarbons (TPH); n-Alkanes; leaf waxes; amendments.
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Abstract
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Plant residues are the main source of organic matter in soil: this process takes place naturally in
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forests and with organic amendments in farmlands. Terrestrial plants also synthesize
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hydrocarbons: typically, angiosperms contain hundreds to thousands mg kg-1 of long-chain n-
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alkanes in leaf waxes. However, petroleum pollution is a worldwide issue and different national
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regulations set at 50 mg kg-1 the guideline limit for petroleum hydrocarbons in green areas.
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Focusing on the Italian legislation as a case study, we hypothesized that direct or indirect high
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inputs of plant residues could lead the soil to exceed this limit, resulting in a false positive
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petroleum contamination. Therefore, we investigated the occurrence of hydrocarbons in soils with
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different inputs of natural or farming biomasses. The highest total petroleum hydrocarbons (TPH)
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concentrations were found in background soils from protected woodlands, remarkably with most
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samples resulting above the guideline limit. Similarly, TPH in agricultural soils amended with
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compost and digestate resulted higher than in soil samples where only chemical fertilizers were
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used. n-Alkanes Carbon Preference Indices (CPIs) underlined the role of plant residues as source of
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hydrocarbons in these samples, clearly distinguishing spiked petrogenic contamination. Possible
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revisions of the regulatory and analytical methods were later discussed.
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Introduction
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Terrestrial plants produce hydrocarbons as components of the epicuticular waxes to protect plant
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tissues from the external environment1. When plant residues are incorporated in soil, these
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contribute to the soil organic matter2, both naturally in woodlands and forests or artificially from
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crop residues or manure in agricultural lands. The input of biomasses and the fertilization with
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amendments, as compost and digestate, have positive effects on the biological, physical, and
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chemical soil properties, reducing dumping of wastes in landfill sites3–5. Moreover, the organic
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matter in agricultural soils is considered one potential sink for sequestration of atmospheric
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carbon dioxide2,6.
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On the other hand, petroleum hydrocarbons are some of the most widespread soil pollutants
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worldwide and hydrocarbon contamination of soil is an issue widely studied in the scientific
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literature. However, one of the main analytical and legal issues is how to distinguish between
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actual petrogenic contamination from naturally occurring hydrocarbons and biogenic 2 ACS Paragon Plus Environment
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interferences, since these could potentially lead to unnecessary remediation costs7. However,
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although many parameters (reported in the SI) have been proposed and used to identify the
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environmental contamination due to petroleum hydrocarbons8–11, none of them is unique and
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effective for the different petroleum-derived products, probably except total petroleum
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hydrocarbons (TPH). This parameter, despite its selectivity drawbacks7, is generally adopted to
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assess the soil contamination from the different petroleum products. The analytical determination
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of TPH includes a large family of different hydrocarbons, regardless of their toxicity, origin and
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composition (linear, branched, cyclic and aromatic compounds)12,13. Italian legislation (Legislative
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Decree 152/2006, Part IV, Title V, Annex 5) sets the limit for heavy hydrocarbons (with a number
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of carbon atoms higher than 12) in public, private, residential green areas and agricultural land at
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50 mg kg-1 d.w.; those sites found to exceed these limits should be remediated or a site-specific
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risk analysis should prove the absence of human health risks. The parameter C>12 is substantially
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corresponding to TPH, defining a slight modification of the normed analytical method ISO
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16703:2004 changing the application range from C10-C40 to C12-C40 13.
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The limit at 50 mg kg-1 d.w. is not based on hydrocarbon toxicity, which is highly dependent on the
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speciation and the availability of the hydrocarbons, but it was selected because it was considered
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to be high enough to avoid false positives14. Consequently this value was chosen as target value
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for soil quality standards in different European countries12,14. However, the various national
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regulations result in very different procedures and intervention guidelines for remediation of
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contamination episodes of agricultural soil. For example, there is a wide discrepancy of two orders
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of magnitude between the Italian and Dutch intervention values for remediation of hydrocarbons
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in soil, being the limits set at 50 mg kg-1 and 5000 mg kg-1 (VROM 2012), respectively12. This clearly
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shows the need for the harmonization of national procedures for contaminated sites in the
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European Union14. Outside from Europe, a similar situation is present also in the USA, with
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significant variability of methods, action and clean-up levels for hydrocarbons in contaminated
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soils among the different states, in a framework of increasing complexity15. The Canadian
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legislation specifies different carbon ranges to analyze the total hydrocarbons in soil7. Notably the
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method does not include a purification step, therefore also polar biogenic compounds such as
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plant waxes, fatty acids and sterols are considered as petroleum hydrocarbon contaminants, even
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when naturally exceeding the regulatory levels16.
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Plant-derived n-alkanes
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Terrestrial plants typically synthesize long chain n-alkanes as part of the epicuticular leaf wax,
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contributing to the hydrophobic properties and protecting the leaf from the external environment.
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Leaf n-alkanes are commonly produced with a strong odd-over-even predominance (OEP), and,
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lacking functional groups, are especially long-lived molecules1. For these reasons n-alkanes are
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widely used as biomarkers to reconstruct environmental changes in modern and paleoecological
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studies1,17. The abundance and distribution of the n-alkanes in leaves depend on the plant species,
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the growing season and the environmental conditions (e.g. temperature, moisture, nutrient
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availability, soil properties), varying even within an individual tree1,18. Typically, angiosperms
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produce hundreds to thousands mg of n-alkanes per kg of dry leaf matter, while gymnosperms are
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at orders of magnitude lower. n-C27, n-C29 and n-C31 are the dominant n-alkanes in graminoids and
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woody angiosperms in variable relative abundances1. The Carbon Preference Index (CPI) is a
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definitive measure of biologically synthesized compounds, defining the degree to which odd
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carbon number n-alkanes dominate over even carbon numbers, being the ratio of the sums of
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concentrations of odd and even n-alkane homologues in a given carbon number range19. Mean CPI
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values in leaves of the large majority of modern plant are around 10 although with very large
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variations, being in few cases close or lower than 1, which is the typical CPI value of petrogenic
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inputs1,20. Another parameter is the weighted average of the various carbon chain lengths of the n-
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alkanes, usually defined as the Average Chain Length (ACL=∑(Cnxn)/∑Cn), where Cn is the
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concentration of each n-alkane with n carbon atoms1. Leaf surface waxes can be sources of n-
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alkanes to soil both in woodland and grassland21,22, as well as directly from crop residues in
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agricultural land 23. Other tissues of higher plants (e.g. beech and spruce roots) are characterized
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by short chain (C12 in suoli contaminati, n. 75/2011.; ISPRA - Manuali e Linee Guida: Rome,
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