Target and Nontarget Screening of PFAS in Biosolids, Composts, and Other Organic Waste Products for Land Application in France.

Zwitterionic, cationic, and anionic per- and polyfluoroalkyl substances (PFAS) are increasingly reported in terrestrial and aquatic environments, but their inputs to agricultural lands are not fully understood. Here, we characterized PFAS in 47 organic waste products (OWP) applied in agricultural fields of France, including historical and recent materials. Overall, 160 PFAS from 42 classes were detected from target screening and homologue-based nontarget screening. Target PFAS were low in agriculture-derived wastes such as pig slurry, poultry manure, or dairy cattle manure (median ∑46PFAS: 0.66 µg/kg dry matter). Higher PFAS levels were reported in urban and industrial wastes, paper mill sludge, sewage sludge, or residual household waste composts (median ∑46PFAS: 220 µg/kg). Historical municipal biosolids and composts (1976-1998) were dominated by perfluorooctanesulfonate (PFOS), N-ethyl perfluorooctanesulfonamido acetic acid (EtFOSAA), and cationic and zwitterionic electrochemical fluorination precursors to PFOS. Contemporaneous urban OWP (2009-2017) were rather dominated by zwitterionic fluorotelomers, which represented on average 55% of ∑160PFAS (max: 97%). The fluorotelomer sulfonamidopropyl betaines (X:2 FTSA-PrB, median: 110 µg/kg, max: 1300 µg/kg) were the emerging class with the highest occurrence and prevalence in contemporary urban OWP. They were also detected as early as 1985. The study informs for the first time that urban sludges and composts can be a significant repository of zwitterionic and cationic PFAS.

Mass balance and long-term soil accumulation of trace elements in arable crop systems amended with urban composts or cattle manure during 17 years.

Organic waste products (OWP) application to crop lands makes possible nutrients recycling. However, it can result in long-term accumulation of trace elements (TE) in soils. The present study aimed at (i) assessing the impact of regular applications of urban composts and manure on the TE contents of topsoils and crops in a long-term field experiment, (ii) comparing the TE mass balances with the stock variations of TE in soils, and (iii) proposing a prospective evaluation of this practice, based on estimated soil safe threshold values and simulations of soil TE accumulation for 100 years. In the long-term field experiment, physico-chemical properties and TE contents (Cd, Cr, Cu, Hg, Ni, Pb and Zn) have been measured in OWP, soils, plants and leaching waters for the period 1998-2015, and used for mass balance calculations and long-term simulations of TE accumulations. The composts of green wastes and sludge (GWS) and of municipal solid waste (MSW) were the OWP with the largest TE contents, while the farmyard manure tended to have the lowest. Repeated application of OWP led to significant accumulation of Zn and Cu in the topsoil layer (not for Cr, Cd, Hg, Ni, Pb), especially with GWS, without overpassing calculated protective threshold values. No effect of repeated application of OWP has been observed on TE contents in grains (wheat, maize, barley). The positive mass balance has been dominated by the input flux of TE through OWP and resulted in the observed increases of soil stocks for Cu and Zn. Prospective simulation of soil content evolution until 2100 showed that soil content reached 0.4 mg Cd kg-1 soil (GWS, MSW), 38 mg Cu kg-1 soil (GWS) and 109 mg Zn kg-1 soil (GWS), which remained lower than protective threshold values.

Trace metal availability in soil horizons amended with various urban waste composts during 17 years - Monitoring and modelling.

Recycling organic residues in agrosystems presents several benefits but faces the question of contaminants, among them a few trace metals which eventually accumulate in soils following regular applications of organic waste products (OWP) and represent an ecological risk. The increase of total trace metal contents in amended topsoils can be predicted by a mass balance approach, but the evolution of their available fractions is a more intricate issue. We aimed at modelling this evolution by using the dataset of a long-term field experiment of OWP applications (manure and three urban waste composts). Two operationally-defined fractions of 6 trace metals have been quantified in the OWP and amended topsoils between 2002 and 2015: the soluble and potentially available metals, extracted in 0.01 M CaCl2 and 0.05 M EDTA solutions, respectively. The potentially available metals have progressively increased in amended topsoils, at rates depending on elements and types of OWP. For Zn, these increases corresponded in average to inputs of potentially available Zn from OWP. But the soil stocks of potentially available Cu increased faster than from the inputs of EDTA-extractable Cu, showing linear regression slopes between 1.4 and 2.5, depending on OWP type. The influence of OWP has been provisionally interpreted in the light of their efficiency to increase soil organic matter and their inputs of reactive oxides. Soluble copper has increased with repeated amendments. But soluble cadmium, nickel and zinc have generally decreased, as they are influenced by changing soil variables such as pH and organic matter. Statistic models were used to unravel the relationships between soluble and EDTA-extractable metals and other soil variables. For Cu, the most satisfactory models just relate soluble and potentially available Cu. Developing such models could contribute to predict the long-term effects of a precise scenario of agricultural OWP recycling upon available trace metals in soils.

Impact of long-term organic residue recycling in agriculture on soil solution composition and trace metal leaching in soils.

Recycling composted organic residues in agriculture can reduce the need of mineral fertilizers and improve the physicochemical and biological properties of cultivated soils. However, some trace elements may accumulate in soils following repeated applications and impact other compartments of the agrosystems. This study aims at evaluating the long-term impact of such practices on the composition of soil leaching water, especially on trace metal concentrations. The field experiment QualiAgro started in 1998 on typical loess Luvisol of the Paris Basin, with a maize-wheat crop succession and five modalities: spreading of three different urban waste composts, farmyard manure (FYM), and no organic amendment (CTR). Inputs of trace metals have been close to regulatory limits, but supplies of organic matter and nitrogen overpassed common practices. Soil solutions were collected from wick lysimeters at 45 and 100 cm in one plot for each modality, during two drainage periods after the last spreading. Despite wide temporal variations, a significant effect of treatments on major solutes appears at 45 cm: DOC, Ca, K, Mg, Na, nitrate, sulphate and chloride concentrations were higher in most amended plots compared to CTR. Cu concentrations were also significantly higher in leachates of amended plots compared to CTR, whereas no clear effect emerged for Zn. The influence of amendments on solute concentrations appeared weaker at 1 m than at 45 cm, but still significant and positive for major anions and DOC. Average concentrations of Cu and Zn at 1m depth lied in the ranges [2.5; 3.8] and [2.5; 10.5 µg/L], respectively, with values slightly higher for plots amended with sewage sludge compost or FYM than for CTR. However, leaching of both metals was less than 1% of their respective inputs through organic amendments. For Cd, most values were <0.05 µg/L. So, metals added through spreading of compost or manure during 14 years may have increased metal concentrations in leachates of amended plots, in spite of increased soil organic matter, factor of metal retention. Indeed, DOC, also increased by amendments, favours the mobility of Cu; whereas pH variations, depending on treatments, influence negatively the solubility of Zn. Generic adsorption functions of these variables partly explain the variations of trace metal concentrations and helped to unravel the numerous processes induced by regular amendments with organic waste products.

RHIZOtest: a plant-based biotest to account for rhizosphere processes when assessing copper bioavailability.

The ability of the free ion activity model (FIAM), the terrestrial biotic ligand model (TBLM), the diffusive gradients in thin films (DGT) technique and a plant-based biotest, the RHIZOtest, to predict root copper (Cu) concentration in field-grown durum wheat (Triticum turgidum durum L.) was assessed on 44 soils varying in pH (3.9-7.8) and total Cu (32-184 mg kg(-1)). None of the methods adequately predicted root Cu concentration, which was mainly correlated with total soil Cu. Results from DGT measurements and even more so FIAM prediction were negatively correlated with soil pH and over-estimated root Cu concentration in acidic soils. TBLM implementation improved numerically FIAM prediction but still failed to predict adequately root Cu concentration as the TBLM formalism did not considered the rhizosphere alkalisation as observed in situ. In contrast, RHIZOtest measurements accounted for rhizosphere alkalisation and were mainly correlated with total soil Cu.