Ice is an important physical and chemical sink for various pollutants in cold regions. The photodegradation of emerging fluoroquinolone (FQ) antibiotic contaminants with dissolved organic matter (DOM) in ice remains poorly understood. Here, the photodegradation of ciprofloxacin (CIP) and fulvic acid (FA) in different proportions as representative FQ and DOM in ice were investigated. Results suggested that the photodegradation rate constant of CIP in ice was 1.9 times higher than that in water. When CFA/CCIP ≤ 60, promotion was caused by FA sensitization. FA increased the formation rate of cleavage in the piperazine ring and defluorination products. When 60 < CFA/CCIP < 650, the effect of FA on CIP changed from promoting to inhibiting. When 650 ≤ CFA/CCIP ≤ 2600, inhibition was caused by both quenching effects of 143.9%–51.3% and light screening effects of 0%–48.7%. FA inhibited cleavage in the piperazine ring for CIP by the scavenging reaction intermediate of aniline radical cation in ice. When CFA/CCIP > 2600, the light screening effect was greater than the quenching effect. This work provides new insights into how DOM affects the FQ photodegradation with different concentration proportions, which is beneficial for understanding the environmental behaviors of fluorinated pharmaceuticals in cold regions.

Chlorpyrifos (CPF), as an organophosphate insecticide extensively used in the modern agricultural system, has been gradually banned in many countries due to its reported health risks to organisms, including humans. This study used simulated paddy field experiments and carbon-14 tracing to explore the possibility of reducing environmental risks of chlorpyrifos application through appropriate agronomic practice. Results showed ¹⁴C-CPF concentration in rice plants planted in the red soil (RS) was significantly higher than that in black soil (BS) and fluvo-aquic soil (FS). The application of biochar and chicken manure in RS reduced ¹⁴C-CPF accumulation in rice plants, and the content of ¹⁴C-CPF in rice grains decreased by 25% and 50%, respectively. Adding biochar to all three soils reduced the migration of ¹⁴C-CPF, especially in FS with the highest risk of ¹⁴C-CPF migration. The addition of chicken manure in FS reduced the migration of ¹⁴C-CPF and the total residual amount of ¹⁴C-CPF in the soil. In addition, chicken manure treatment increased the formation of ¹⁴C-bound residues (BRs) in soils and changed the distribution ¹⁴C-BRs in humus. The results indicated that the degree of environmental risks associated with the CPF application varies with soil types and could be reduced by introducing suitable exogenous organic matter into different soils, which is of great significance for guiding the scientific application of chlorpyrifos in agronomic practices.

Undissolved humic acid (HA) is known to substantially effect the migration and transformation of hexavalent chromium [Cr(VI)] in soils. The mechanisms of Cr(VI) retention in soils by undissolved HA have been reported; however, past studies are inconclusive about the types of HA functional groups that are involved in Cr(VI) retention and the retention mechanisms. Utilizing a two-dimensional correlation spectroscopy (2DCOS) analysis for FTIR and 13C CP/MAS NMR, this study investigated the variations of HA function groups and molecular structures after reactions with aqueous Cr(VI) under different pH conditions. Based on the changing sequence of functional groups interpreted from the 2DCOS results, a four-step mechanism for Cr(VI) retention was determined as follows: (1) electrostatic adsorption of Cr(VI) to HA surface, (2) complexation of adsorbed Cr(VI) by carboxyl and ester, (3) reduction of complexed Cr(VI) to Cr(III) by phenol and polysaccharide, and (4) complexation of reduced Cr(III) by carboxylic groups. These functional groups that are involved in Cr(VI) retention were determined to occur in aromatic domains.

Mining and smelting activities have contaminated the environment with trace metals (TMs) at a worldwide scale for at least two millennia. A combination of chemical approaches and active biomonitoring was performed to analyse the environmental availability and bioavailability of TM palaeo-pollution in a former PbAg mining district in the Vosges Mountains, France. Along a soil TM contamination gradient that covered eight stations, including two archaeological mining sites, the toxicokinetics of six TMs (Pb, Cd, As, Ag, Co, Sb) in the snail Cantareus aspersus revealed that palaeo-pollution from the studied sites remains bioavailable. This study provides the first data on the accumulation kinetics of Ag and Co for C. aspersus. The environmental availability of the TMs was estimated with three chemical extraction methods (aqua regia, EDTA 50 mM, CaCl2 10 mM). Univariate regression analyses showed that EDTA extraction is the best method for estimating the bioavailability of Pb, As, Ag, Co and Sb to snails. None of the three extractants was efficient for Cd. A multivariate analysis of bioaccumulation data revealed that TM bioavailability and transfer were modulated by exposure sources (soil, humus and vegetation) rather than by soil physico-chemical characteristics. Hence, although the deposition of mining wastes dates back several centuries, these wastes still represent a source of contamination that must be considered to develop relevant site management and environmental risk assessment.

Total cadmium (Cd) concentrations in four ornithogenic coral-sand sedimentary profiles displayed a strong positive correlation with guano-derived phosphorus, but had no correlation with plant-originated organic matter in the top sediments. These results indicate that the total Cd distributions were predominantly controlled by guano input. Bioavailable Cd and zinc (Zn) had a greater input rate in the top sediments with respect to total Cd and total Zn, and a positive correlation with total organic carbon (TOC) derived from plant humus. Multi-regression analysis showed that the total Cd and TOC explained over 80% of the variation of bioavailable Cd, suggesting that both guano and plant inputs could significantly influence the distribution of bioavailable Cd, and that plant biocycling processes contribute more to the recent increase of bioavailable Cd. A pollution assessment indicates that the Yongle archipelago is moderately to strongly polluted with guano-derived Cd.

In forest soils along vertical profiles located in different parts of the Alps, concentrations of persistent organic pollutants (POPs), namely organochlorine pesticides (OCPs) like dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), heptachlor, aldrin, dieldrin and mirex, were measured. Though local characteristics of the sites are influenced by numerous factors like orographic and meteorological parameters, forest stand characteristics and humus parameters, we ascertained a marked vertical increase of concentrations of some organochlorine compounds in the soil. On the basis of climatological values of each site, we found that the contamination increase with altitude can be ascribed to a certain ‘cold condensation effect’. In addition, the perennial atmospheric deposition of POPs is controlled by precipitation. Other key parameters explaining the accumulation of POPs are the soil organic carbon stocks, the turnover times, the re-volatilisation and degradation processes, which vary with altitude. Caused by temperature-dependent processes regarding deposition, re-volatilization and decomposition of POPs, the concentration of organochlorine pesticides varies in the Alpine region with altitude.

2,4-Dinitroanisole (DNAN) is a component of insensitive munitions (IM), which are replacing traditional explosives due to their improved safety. Incomplete IM combustion releases DNAN onto the soil, where it can leach into the subsurface with rainwater, encounter anoxic conditions, and undergo (a)biotic reduction to aromatic amines 2-methoxy-5-nitroaniline (MENA), 4-methoxy-3-nitroaniline (iMENA, isomer of MENA), and 2,4-diaminoanisole (DAAN). We report here studies of nucleophilic addition mechanisms that may account for the sequestration of aromatic amine daughter products of DNAN into soil organic matter (humus), effectively removing these toxic compounds from the aqueous environment. Because quinones are important moieties in humus, we incubated MENA, iMENA, DAAN, and related analogs with model compounds 1,4-benzoquinone and 2,3-dimethyl-1,4-benzoquinone under anoxic conditions. Mass spectrometry and ultra-high performance liquid chromatography revealed that the aromatic amines had covalently bonded to either carbonyl carbons or ring carbons β to carbonyl carbons of the quinones, producing a mixture of imines and Michael adducts, respectively. These products formed rapidly and accumulated in the one-to four-day incubations. Nucleophilic addition reactions, which do not require catalysis or oxic conditions, are proposed as a mechanism resulting in the binding of DNAN to soil observed in previous studies. To remediate sites contaminated with DNAN or other nitroaromatics, reducing conditions and humus amendments may promote their immobilization into the soil matrix.

The surface organic horizons in forest soils have been affected by air and soil pollutants, including potentially toxic elements (PTEs). Monitoring of PTEs requires a large number of samples and adequate analysis. Visible–near infrared (vis–NIR: 350–2500 nm) spectroscopy provides an alternative method to conventional laboratory measurements, which are time-consuming and expensive. However, vis–NIR spectroscopy relies on an empirical calibration of the target attribute to the spectra. This study examined the capability of vis–NIR spectra coupled with machine learning (ML) techniques (partial least squares regression (PLSR), support vector machine regression (SVMR), and random forest (RF)) and a deep learning (DL) approach called fully connected neural network (FNN) to assess selected PTEs (Cr, Cu, Pb, Zn, and Al) in forest organic horizons. The dataset consists of 2160 samples from 1080 sites in the forests over all the Czech Republic. At each site, we collected two samples from the fragmented (F) and humus (H) organic layers. The content of all PTEs was higher in horizon H compared to F horizon. Our results indicate that the reflectance of samples tended to decrease with increased PTEs concentration. Cr was the most accurately predicted element, regardless of the algorithm used. SVMR provided the best results for assessing the H horizon (R² = 0.88 and RMSE = 3.01 mg/kg for Cr). FNN produced the best predictions of Cr in the combined F + H layers (R² = 0.89 and RMSE = 2.95 mg/kg) possibly due to the larger number of samples. In the F horizon, the PTEs were not predicted adequately. The study shows that PTEs in forest soils of the Czech Republic can be accurately estimated with vis–NIR spectra and ML approaches. Results hint in availability of a large sample size, FNN provides better results.

Three soil core samples were collected from a forest located about 1.1 km south of the Fukushima Daiichi Nuclear Power Plant (FDNPP) boundary in 2017, and the vertical profiles of 129I from the FDNPP accident were determined by the combination of TMAH (tetramethyl ammonium hydroxide) extraction and ICP-MS/MS analysis. The humus layer above the soil layer was heavily contaminated with 134Cs (1983–5985 Bq g−1) and 137Cs (1947–5902 Bq g−1) (decay-corrected to March 11, 2011). The 129I activity concentrations decreased sharply with the soil depth, from 1894 to 34.1, from 9384 to 78.9, and from 2536 to 51.3 mBq kg−1, for the three sites. Downward migration of 129I was slightly faster than the one of 134Cs. In addition, the cumulative 129I inventories were observed to be 43.4 ± 1.0, 71.7 ± 1.8, and 56.5 ± 1.8 Bq m−2, respectively. Subsequently, the cumulative 131I inventories were estimated to be 1.76 ± 0.06, 2.90 ± 0.11, and 2.28 ± 0.10 GBq m−2 (decay-corrected to March 11, 2011), respectively. Finally, the total atmospheric deposition of 129I on the land of Japan due to the FDNPP accident was estimated to be around 1.09–1.71 kg (7.11–11.2 GBq).

Samples of 474 forest stands in Germany were analysed for concentrations of polycyclic aromatic hydrocarbons (PAHs) in three sampling depths. Enhanced concentrations were mainly found at spots relatively close to densely industrialized and urbanized regions and at some topographically elevated areas. Average enrichment factors between mineral soil and humic layer depend on humus type i.e. decrease from mull via moder to mor. Based on their compound-patterns, the observed samples could be assigned to three main clusters. For some parts of our study area a uniform assignment of samples to clusters over larger regions could be identified. For instance, samples taken at vicinity to brown-coal strip-mining districts are characterized by high relative abundances of low-molecular-weight PAHs. These results suggest that PAHs are more likely originated from local and regional emitters rather than from long-range transport and that specific source-regions can be identified based on PAH fingerprints.