Forest and agricultural land use affects the concentration and composition of dissolved organic carbon (DOC) in streams and rivers. To elucidate the impacts of forest and agricultural land use on stream DOC during storm events, we investigated DOC concentration ([DOC]), optical properties of dissolved organic matter (DOM), and Δ¹⁴C-DOC in both forest- and agriculture-dominated headwater streams in South Korea in the summer of 2012. One forested and five agricultural streams were investigated. During storms, the peak [DOC] of forest stream increased to 5.8 mg L⁻¹, approximately two times larger than that of the most agricultural stream (3.2 mg L⁻¹), demonstrating the weaker storm responses of the [DOC] of agricultural streams to hydrological change. Five PARAFAC components were identified, including three terrestrial humic-like substances (C1, C2, C3), one microbial humic substance (C4), and one microbial protein-like substances (C5). The mean (C4+C5)/(C1+C2+C3) of all storm events at the most agricultural stream was 1.5 times larger than that of the most forested stream, suggesting that more protein-like DOM is exported from agricultural watersheds. Whereas a forest stream was primarily composed of terrestrially derived and ¹⁴C-enriched modern DOC, the ¹⁴C-age of the most agricultural stream was up to ∼1000 years old. The results suggest that agricultural practices could decrease the old organic carbon pools from soils. However, how quickly the aged DOC can be degraded to CO₂ in streams is unknown, warranting future investigation on lability of the aged DOC and their effects on CO₂ evasion from rivers and estuaries downstream.

Atmospheric nitrogen (N) deposition is believed to accelerate dissolved organic carbon (DOC) production and could lead to increased heavy metal mobility into water resources. We sampled intact soil cores from the Isle of Skye with low background N deposition history and having Serpentine rock known for its higher heavy metal concentrations including zinc (Zn), copper (Cu), nickel (Ni) and lead (Pb). The effects of 16 (16kgN) and 32 kg N ha⁻¹ year⁻¹ (32kgN), and liming with 32kgN (32kgN+Lime) on soil solution chemistry and heavy metal mobilization were investigated over the 15-month study. Nitrogen in deposition load was added at five ammonium (NH₄⁺) to nitrate (NO₃⁻) ratios of 9:1, 5:1, 1:1, 1:5 and 1:9 along NO₃⁻dominance. We found significant effects of load on Cu and NH₄⁺/NO₃⁻ ratio on pH, DOC and Zn in soil solution. However, under lime and ratio experimental factors, liming significantly influenced pH, DOC, Cu and Pb, and NH₄⁺/NO₃⁻ ratio pH, DOC, Ni and Zn whereas interactions between lime and ratio was significant for Ni and Cu. pH and DOC increased with N load, liming and NO₃⁻ dominance, and both correlated significantly positively. Liming under NH₄⁺ dominance enhanced DOC production due to supply of base cations in lime. Mobilization of Cu, Ni and Pb was driven by DOC concentrations and, therefore, increased with load, liming and NO₃⁻ dominance in deposition. However, in contrast, low pH and high NH₄⁺ dominance was associated with Zn mobilization in soil solution. On the contrary, despite of some patterns, heavy metals in soil HNO₃ extracts were devoid of any load, lime and NH₄⁺/NO₃⁻ ratio effects. Our study suggests that the effects of N load and forms in deposition on sites with high accumulated loads of metals need to be better quantified through soil solution partitioning models.

Tools to predict environmental fate processes during remediation of persistent organic pollutants (POPs) in soil are desperately needed since they can elucidate the overall behavior of the chemical and help to improve the remediation process. A dynamic multimedia fate model (SoilPlusVeg) was further developed and improved to account for rhizoremediation processes. The resulting model was used to predict Polychlorinated Biphenyl (PCB) fate in a highly contaminated agricultural field (1089 ng/g d.w.) treated with tall fescue (Festuca arundinacea), a promising plant species for the remediation of contaminated soils. The model simulations allowed to calculate the rhizoremediation time (about 90 years), given the available rhizoremediation half-lives and the levels and fingerprints of the PCB congeners, to reach the legal threshold, to show the relevance of the loss processes from soil (in order of importance: degradation, infiltration, volatilization, etc.) and their dependence on meteorological and environmental dynamics (temperature, rainfall, DOC concentrations). The simulations showed that the effective persistence of PCBs in soil is deeply influenced by the seasonal variability. The model also allowed to evaluate the role of DOC as a possible enhancer of PCB degradation as a microorganism “spoon feeder” of PCBs in the soil solution. Additionally, we preliminary predicted how the contribution of PCB metabolites could modify the PCB fingerprint and their final total concentrations. This shows that the SoilPlusVeg model could be used in selecting the best choices for a sustainable rhizoremediation of a POP contaminated site.

Increased reactive nitrogen (N) loadings to terrestrial ecosystems are believed to have positive effects on ecosystem carbon (C) sequestration. Global “hot spots” of N deposition are often associated with currently or formerly high deposition of sulphur (S); C fluxes in these regions might therefore not be responding solely to N loading, and could be undergoing transient change as S inputs change. In a four-year, two-forest stand (mature Norway spruce and European beech) replicated field experiment involving acidity manipulation (sulphuric acid addition), N addition (NH4NO3) and combined treatments, we tested the extent to which altered soil solution acidity or/and soil N availability affected the concentration of soil dissolved organic carbon (DOC), soil respiration (Rs), microbial community characteristics (respiration, biomass, fungi and bacteria abundances) and enzyme activity. We demonstrated a large and consistent suppression of soil water DOC concentration driven by chemical changes associated with increased hydrogen ion concentrations under acid treatments, independent of forest type. Soil respiration was suppressed by sulphuric acid addition in the spruce forest, accompanied by reduced microbial biomass, increased fungal:bacterial ratios and increased C to N enzyme ratios. We did not observe equivalent effects of sulphuric acid treatments on Rs in the beech forest, where microbial activity appeared to be more tightly linked to N acquisition. The only changes in C cycling following N addition were increased C to N enzyme ratios, with no impact on C fluxes (either Rs or DOC). We conclude that C accumulation previously attributed solely to N deposition could be partly attributable to their simultaneous acidification.

Cyclophosphamide (CP) and ifosfamide (IF) are commonly used cytostatic drugs that repress cell division by interaction with DNA. The present study investigates the ecotoxicity and genotoxicity of CP, IF, their human metabolites/transformation products (TPs) carboxy-cyclophosphamide (CPCOOH), keto-cyclophosphamide (ketoCP) and N-dechloroethyl-cyclophosphamide (NdCP) as individual compounds and as mixture. The two parent compounds (CP and IF), at concentrations up to 320 mg L−1, were non-toxic towards the alga Pseudokirchneriella subcapitata and cyanobacterium Synecococcus leopoliensis. Further ecotoxicity studies of metabolites/TPs and a mixture of parent compounds and metabolites/TPs performed in cyanobacteria S. leopoliensis, showed that only CPCOOH (EC50 = 17.1 mg L−1) was toxic. The measured toxicity (EC50 = 11.5 mg L−1) of the mixture was lower from the toxicity predicted by concentration addition model (EC50 = 21.1 mg L−1) indicating potentiating effects of the CPCOOH toxicity. The SOS/umuC assay with Salmonella typhimurium revealed genotoxic activity of CP, CPCOOH and the mixture in the presence of S9 metabolic activation. Only CPCOOH was genotoxic also in the absence of metabolic activation indicating that this compound is a direct acting genotoxin. This finding is of particular importance as in the environment such compounds can directly affect DNA of non-target organisms and also explains toxicity of CPCOOH against cyanobacteria S. leopoliensis. The degradation study with UV irradiation of samples containing CP and IF showed efficient degradation of both compounds and remained non-toxic towards S. leopoliensis, suggesting that no stable TPs with adverse effects were formed. To our knowledge, this is the first study describing the ecotoxicity and genotoxicity of the commonly used cytostatics CP and IF, their known metabolites/TPs and their mixture. The results indicate the importance of toxicological evaluation and monitoring of drug metabolites as they may be for certain aquatic species more hazardous than parent compounds.

Discharge of antimicrobial residues and resistant bacteria in hospital effluents is supposed to have strong impacts on the spread of antibiotic resistant bacteria in the environment. This study aimed to characterize the effluents of the Gabriel Montpied teaching hospital, Clermont-Ferrand, France, by simultaneously measuring the concentration of ciprofloxacin and of biological indicators resistant to this molecule in biofilms formed in the hospital effluent and by comparing these data to ciprofloxacin consumption and resistant bacterial isolates of the hospital. Determination of the measured environmental concentration of ciprofloxacin by spot sampling and polar organic chemical integrative (POCIS) sampling over 2 weeks, and comparison with predicted environmental concentrations produced a hazard quotient >1, indicating a potential ecotoxicological risk. A negative impact was also observed with whole hospital effluent samples using the Tetrahymena pyriformis biological model.During the same period, biofilms were formed within the hospital effluent, and analysis of ciprofloxacin-resistant isolates indicated that Gamma-Proteobacteria were numerous, predominantly Aeromonadaceae (69.56%) and Enterobacteriaceae (22.61%). Among the 115 isolates collected, plasmid-mediated fluoroquinolone-resistant genes were detected, with mostly aac(6′)-lb-cr and qnrS. In addition, 60% of the isolates were resistant to up to six antibiotics, including molecules mostly used in the hospital (aminosides and third-generation cephalosporins).In parallel, 1247 bacteria isolated from hospitalized patients and resistant to at least one of the fluoroquinolones were collected. Only 5 of the 14 species identified in the effluent biofilm were also found in the clinical isolates, but PFGE typing of the Gram-negative isolates found in both compartments showed there was no clonality among the strains.Altogether, these data confirm the role of hospital loads as sources of pollution for wastewater and question the role of environmental biofilms communities as efficient shelters for hospital-released resistance genes.

Southeastern Alaska is a remote coastal-maritime ecosystem that is experiencing increased deposition of mercury (Hg) as well as rapid glacier loss. Here we present the results of the first reported survey of total and methyl Hg (MeHg) concentrations in regional streams and biota. Overall, streams draining large wetland areas had higher Hg concentrations in water, mayflies, and juvenile salmon than those from glacially-influenced or recently deglaciated watersheds. Filtered MeHg was positively correlated with wetland abundance. Aqueous Hg occurred predominantly in the particulate fraction of glacier streams but in the filtered fraction of wetland-rich streams. Colonization by anadromous salmon in both glacier and wetland-rich streams may be contributing additional marine-derived Hg. The spatial distribution of Hg in the range of streams presented here shows that watersheds are variably, yet fairly predictably, sensitive to atmospheric and marine inputs of Hg.

Biochar-oxalic acid composite application (BCOA) have shown to be efficient in the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soil, but the functional degraders and the mechanism of improving biodegradation remains unclear. In this study, with the help of stable isotope probing technology of phenanthrene (Phe), we determined that BCOA significantly improved Phe mineralization by 2.1 times, which was ascribed to the increased numbers and abundances of functional degraders. The BCOA increased contents of dissolved organic carbon and available nutrients and decreased pH values in soil, thus promoting the activity, diversity and close cooperation of the functional Phe-degraders, and stimulating their functions associated with Phe degradation. In addition, there is a relay activity among more and diverse functional Phe-degraders in the soil with BCOA. Specifically, Pullulanibacillus persistently participated in Phe-degradation in the soil with BCOA throughout the incubation period. Moreover, Pullulanibacillus, Blastococcus, Alsobacter, Ramlibacter, and Mizugakiibacter were proved to be potential Phe-degraders in soil for the first time. The specific Phe degraders and their relay and cooperation activity in soils as impacted by BCOA were first identified with DNA-stable isotope probing technology. Our findings provided a novel perspective to understand the efficient degradation of PAH in the BCOA treatments, revealed the potential of soil native microbes in the efficient bioremediation of PAH-contaminated natural soil, and provided a basis for the development of in-situ phytoremediation technologies to remediate PAH pollution in future.

Reservoirs typically have elevated fish mercury (Hg) levels compared to natural lakes and rivers. A unique feature of reservoirs is water-level management which can result in sediment exposure to the air. The objective of this study is to identify how reservoir water-level fluctuations impact Hg cycling, particularly the formation of the more toxic and bioaccumulative methylmercury (MeHg). Total-Hg (THg), MeHg, stable isotope methylation rates and several ancillary parameters were measured in reservoir sediments (including some in porewater and overlying water) that are seasonally and permanently inundated. The results showed that sediment and porewater MeHg concentrations were over 3-times higher in areas experiencing water-level fluctuations compared to permanently inundated sediments. Analysis of the data suggest that the enhanced breakdown of organic matter in sediments experiencing water-level fluctuations has a two-fold effect on stimulating Hg methylation: 1) it increases the partitioning of inorganic Hg from the solid phase into the porewater phase (lower log Kd values) where it is more bioavailable for methylation; and 2) it increases dissolved organic carbon (DOC) in the porewater which can stimulate the microbial community that can methylate Hg. Sulfate concentrations and cycling were enhanced in the seasonally inundated sediments and may have also contributed to increased MeHg production. Overall, our results suggest that reservoir management actions can have an impact on the sediment-porewater characteristics that affect MeHg production. Such findings are also relevant to natural water systems that experience wetting and drying cycles, such as floodplains and ombrotrophic wetlands.

Catchments draining peat soils provide the majority of drinking water in the UK. Over the past decades, concentrations of dissolved organic carbon (DOC) have increased in surface waters. Residual DOC can cause harmful carcinogenic disinfection by-products to form during water treatment processes. Increased frequency and severity of droughts combined with and increased temperatures expected as the climate changes, have potentials to change water quality. We used a novel approach to investigate links between climate change, DOC release and subsequent effects on drinking water treatment. We designed a climate manipulation experiment to simulate projected climate changes and monitored releases from peat soil and litter, then simulated coagulation used in water treatment. We showed that the ‘drought’ simulation was the dominant factor altering DOC release and affected the ability to remove DOC. Our results imply that future short-term drought events could have a greater impact than increased temperature on DOC treatability.