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.

Taking advantage of the different histories of Hg deposition in Davos Seehornwald in E-Switzerland and Changbai Mountain in NE-China, the influence of atmospheric deposition on Hg soil dynamics in forest soil profiles was investigated. Today, Hg fluxes in bulk precipitation were similar, and soil profiles were generally sinks for atmospherically deposited Hg at both sites. Noticeably, a net release of 2.07 μg Hg m⁻² yr⁻¹ from the Bs horizon (Podzol) in Seehornwald was highlighted, where Hg concentration (up to 73.9 μg kg⁻¹) and soil storage (100 mg m⁻³) peaked. Sequential extraction revealed that organic matter and crystalline Fe and Al hydr (oxide)-associated Hg decreased in the E horizon but increased in the Bs horizon as compared to the Ah horizon, demonstrating the coupling of Hg dynamics with the podzolisation process and accumulation of legacy Hg deposited last century in the Bs horizon. The mor humus in Seehornwald allowed Hg enrichment in the forest floor (182–269 μg kg⁻¹). In Changbai Mountain, the Hg concentrations in the Cambisol surface layer with mull humus were markedly lower (<148 μg kg⁻¹), but with much higher Hg soil storage (54–120 mg m⁻³) than in the Seehornwald forest floor (18–27 mg m⁻³). Thus, the vertical distribution pattern of Hg was influenced by humus form and soil type. The concentrations of Hg in soil porewater in Seehornwald (3.4–101 ng L⁻¹) and in runoff of Changbai Mountain (1.26–5.62 ng L⁻¹) were all low. Moreover, the pools of readily extractable Hg in the soils at both sites were all <2% of total Hg. Therefore, the potential of Hg release from the forest soil profile to the adjacent aquatic environment is currently low at both sites.

Eutrophication is an important water environment issue facing global lakes. Diversion of water from external watersheds into lakes is considered as effective in ameliorating eutrophication and reducing algal blooms. Nevertheless, the changes in lake water environment caused by external water diversion, especially the influence of water diversion on the characteristics of dissolved organic matters (DOM), are still poorly understood. We therefore used a combination of EEM-PARAFAC, Principal Component Analysis (PCA), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to investigate the effects of water diversion from the Niulan River on DOM characteristics in Lake Dianchi. The results showed that the water diversion from the Niulan River significantly improved the water quality of Lake Dianchi, the concentrations of TN, TP, COD and Chla decreased rapidly, and the degree of humification of dissolved organic matter (DOM) increased, which was in sharp contrast with that of pre-implementation. Firstly, the diversion of water from the Niulan River mainly led to changes in the structure of pollution sources. The load of influent rivers and sewage treatment plants rich in lignin and tannins increased, and the input of terrestrial humus increased. Second, the improved water quality reduced algal enrichment and frequency of blooms, and reduced the release of lipid- and protein-riched algal-derived DOM. Finally, the hydraulic retention time of Lake Dianchi caused by water diversion was shortened, the hydrodynamic conditions were significantly improved, and the dissolved oxygen (DO) level gradually recovered, which played a positive role in improving the humification degree of DOM. Our findings provide new insights for exploring the improvement of eutrophic lake eco-environmental quality caused by water diversion projects.

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.

Increasing amount of aluminum (Al) gets into aquatic ecosystem through anthropogenic activity, but the knowledge about Al migration and relationships with sediments possessing different physico-chemical properties in eutrophic lakes is limited. Here, the Al migration rule and relationships with sediment nutritions in the Hangzhou West Lake, China was investigated, where a certain amount of residual Al-salts can enter because of the pre-treatment of the Qiantang River diversion project every day. Results revealed the obvious spatial distribution heterogeneity of Al in sediment vertical direction and horizontal direction following water flow. The Al content in sediment ranged 0.463–1.154 g kg⁻¹ in Maojiabu Lake, and ranged 9.862–40.442 g kg⁻¹ in Xiaonanhu Lake. Higher Al content distributed in upper layer sediment in lake with more disturbance. Total nitrogen (TN) contents were higher 0.917–3.387 mg g⁻¹ and 0.627–0.786 mg g⁻¹ in upper layer sediment than that in lower layer in Maojiabu Lake and Xiaonanhu Lake, respectively. Total phosphorus (TP) content ranged 0.779–2.580 mg g⁻¹, in which IP and Fe/Al-P contributed 24.9–80.8% and 17.0–51.6%, respectively. Correlations between Al content with nutrition, humic acid (HA) etc. of sediment regionally varied in Maojiabu and Xiaonanhu Lake. Spatial distribution of Al-salt in eutrophic lakes closely related with the physico-chemical characteristics of nutrients, humus, human disturbance and water division parameters. Results provides new insight into Al-salts migration and references for Al-risk evaluating in eutrophic lakes.

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.

PCDD/F and PCB concentrations in remote mountainous spruce stands of the Central European Alps show strong geographic variation. Independent of the matrix (0.5 year old needles, humus or mineral soil), the highest pollutant levels were always found at the lateral zones of the mountain range. High levels coincided with strong precipitation, particularly along the northern margin of the study region. The most volatile PCB congener propagated farther into the colder, drier central Alps than the heavier species. Matrices with different accumulation history (needles and humus) repeatedly reflected different spatial immission patterns. Consistent with its much longer exposure, pollutant levels in humus exceeded those of needles by up to two orders of magnitude. Needle contamination varied with altitude but the vertical trends were highly variable between transsects and changed between years, too. Dioxin-like pollution of forests in the Alps shows strong geographic variation.

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.

Chlorinated paraffins (CPs) are toxic, bioaccumulative, persistent, and ubiquitously present in the environment. CPs were analyzed in humus and needle samples, which were taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) at sampling sites of 7 different altitude profiles in the Alps. Gas chromatography combined with electron ionization tandem mass spectrometry (EI-MS/MS) was used for the determination of total CPs (sum of short, medium and long chain CPs). CPs were found in all samples; the concentrations varied between 7 and 199 ng g−1 dry weight (dw) and within 26 and 460 ng g−1 dw in humus and needle samples, respectively. A clear vertical tendency within the individual altitude profiles could not be ascertained. Within all altitude profiles, elevated concentrations were observed in humus samples taken between 700 and 900 m and between 1300 and 1500 m. In the needle samples no similar correlation could be observed due to higher variation of the data. For the first time, CP levels of humus and spruce needle samples from the Alps (MONARPOP) were presented including the evaluation of altitude profiles.

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.