Automated Method for the Sensitive Analysis of Volatile Amines in Seawater.

Methylamines are polar, volatile, and organic nitrogen-containing compounds. They are challenging to analyze, limiting our understanding of their occurrence and role within the marine nitrogen cycle. We describe an automated headspace solid-phase microextraction method, coupled with gas chromatography and nitrogen phosphorus detection (HS-SPME-GC-NPD), for analyzing methylamines in seawater. Three SPME conditions were investigated: temperature, equilibration, and extraction. The method was 6-24 times more sensitive to trimethylamine (TMA) than to dimethylamine (DMA) and monomethylamine (MMA). DMA and TMA were detected in small seawater volumes (2.5-10 mL), at volumes 100-400 times that previously reported. Detection limits of 19.1, 6.6, and 4.1 nM (nMol L-1) for MMA, DMA, and TMA, respectively, were measured in 10 mL sample volumes. Sample throughput was 4-6 times greater than previously reported similar methods. According to the Blue Applicability Grade Index (BAGI) metric, the method was considered "practical" and scored 62.5. The method was used to measure methylamines in seawater samples collected from the Southern Ocean. DMA and TMA were detected at concentrations from < LoD-35 nM and < LoD-48 nM, respectively. This study offers a systematic and standardized method for MA analysis in seawater and can significantly advance understanding of their role in marine systems.

Inorganic phosphorous availability and mobility in a manufactured soil.

Manufactured soils, created by combining various organic and inorganic waste materials and byproducts, may be tailored to specific applications, providing an alternative to the extraction of natural soils. It is important for them to be capable of supporting plant growth without the need for significant management or fertiliser applications, the over-application of which can have adverse environmental effects. We examined the dynamics of phosphorus (P) transformations within a manufactured soil and the implications for nutrient cycling. A freshly prepared manufactured soil (32.5 % composted green waste, 32.5 % composted bark, 25 % horticultural grit, and 10 % lignite clay) was studied over one year in temperature and moisture controlled mesocosms. Leachate was collected to achieve high-resolution monitoring of leached phosphate concentrations. Initially, leached dissolved inorganic phosphorus (DIP) concentrations were low (0.02 ± 0.01 mg P L-1), before increasing by 160 µg P L-1 d-1 over the first 42 days to 5.57 ± 1.23 mg P L-1. After reaching a maximum concentration, DIP concentrations remained relatively consistent, varying by only 1.67 mg P L-1 until day 270. The increase in leached DIP was likely driven by soil organic matter mineralisation and the cleavage of carbon­phosphorus bonds by the soil microbes to satisfy carbon demand with mineralogical influences, such as a decrease in apatite content, also contributing. Sorption and desorption from soil particles were the processes behind the P loss from the soil, which was followed by slow diffusion and eventual loss via leaching. The fertiliser application on phosphate dynamics resulted in increased DIP leaching. P concentrations observed in the manufactured soil were within the range considered sufficient to support plant growth. However, the mean leached phosphorus concentrations were higher than reported eutrophication thresholds suggesting that these soils may pose a risk to surface waters in their current form.

Biochar improves fertility in waste derived manufactured soils, but not resilience to climate change.

We present a soil manufactured from waste materials, which could replace the use of peat and topsoil in plant production and reduce the pressure on natural soil resources. We tested the effect of the manufactured soil on ecosystem functions and microbial communities with and without plants present, and with and without biochar addition (Experiment 1). The resilience of the soil in response to drought and flooding, and also the effect of biochar was also tested (Experiment 2). Biochar increased soil C and N regardless of plant presence and negated the effect of the plant on soil peroxidase enzyme activity. The manufactured soil was largely resilient to drought, but not flooding, with negative impacts on microbial communities. Results indicate that biochar could improve soil properties, but not resilience to climatic perturbations. Results suggest that manufactured soils amended with biochar could offer a useful alternative to natural soil in many contexts.

The determination of volatile amines in aquatic marine systems: A review.

This review provides a critical assessment of knowledge regarding the determination of volatile, low molecular weight amines, and particularly methylamines, in marine aquatic; systems. It provides context for the motivation to determine methylamines in the marine aquatic environment and the analytical challenges associated with their measurement.While sensitive analytical methods have been reported in recent decades, they have not been adopted by the oceanographic community to investigate methylamines' biogeochemistry and advance understanding of these analytes to the degree achieved for other marine volatiles. Gas chromatography, high performance liquid chromatography, ion chromatography and infusion-mass spectrometry techniques are discussed and critically determined, alongside offline and online preconcentration steps. Interest in the marine occurrence and cycling of methylamines has increased within the last 10-15 years, due to their potential role in climate regulation. As such, the need for robust, reproducible methods to elucidate biogeochemical cycles for nitrogen and populate marine models is apparent. Recommendations are made as to what equipment would be most suitable for future research in this area.

Uptake, accumulation and impact of antiretroviral and antiviral pharmaceutical compounds in lettuce.

While the contamination of agroecosystems with pharmaceutical compounds has been reported, the fate of these compounds, particularly uptake into plants remains unclear. This lack of environmental fate data is evident for a critical class of pharmaceuticals, the antivirals and antiretrovirals (ARVDs). Thus, this study evaluated the root uptake of the antiretroviral compounds nevirapine, lamivudine and efavirenz, and the antiviral compound oseltamivir in lettuce. The lettuce was hydroponically grown in a nutrient solution containing the four ARVD pharmaceutical mixture in the 1-100 µg L-1 concentration range. The measured bioaccumulation showed that efavirenz and lamivudine accumulated to the highest and lowest degree, at concentrations of 3463 ng g-1 and 691 ng g-1 respectively. The translocation factor between the root and leaf for nevirapine was greater than 1. The highest concentration of the pharmaceutical mixture had a physiological impact on the lettuce. Potential toxicity was evidenced by a statistically significant 34% (p = 0.04) mean reduction in root and leaf biomass in the 100 µg L-1 ARVD mix exposed lettuce, compared with the controls. This study advances knowledge of the fate of ARVDs in agroecosystems, in particular, plant root - ARVD interaction and the resulting potentially toxic effects on plants.

Developing the OECD 106 fate testing protocol for active pharmaceuticals in soil.

The ability to determine accurately the fate of APIs in soil is essential for rigorous risk assessment associated with wastewater reuse or biosolid recycling to land, particularly in lower income countries where water and fertiliser is scarce. Four APIs (naproxen, ofloxacin, propranolol and nevirapine) with wide ranging functionality were used as examples in the development of the OECD 106 soil partitioning and/or degradation study, with naproxen used to illustrate applying the full methodology. The data showed key methodological criteria require careful consideration and testing to generate accurate and consistent results. Only glass fibre membranes were suitable for all APIs, without unduly adsorbing APIs to their surface, thus effectively restricting the minimum practical pore size to 0.7 µm. Polypropylene plastic centrifuge tubes were shown to be suitable, with careful determination of recoveries. Direct injection liquid chromatography-mass spectrometry could reliably resolve all 4 APIs down to less than µg L-1 in soil solutions, although allowance for matrix effects via standard additions was required in some cases. Greatest analytical challenges were found for the highest molecular weight API with the greatest affinity for sorption to surfaces (ofloxacin). Key variables that can impact on partitioning such as solution pH and dissolved organic carbon concentrations were shown to vary within tests over time and should be accounted for.

Characterization of the Nairobi River catchment impact zone and occurrence of pharmaceuticals: Implications for an impact zone inclusive environmental risk assessment.

The largely uncontrolled release of active pharmaceuticals ingredients (APIs) within untreated wastewater discharged to waterbodies, associated with many rapidly urbanising centres is of growing concern owing to potential antimicrobial resistance, endocrine disruption and potential toxicity. A sampling campaign has been undertaken to assess the source, occurrence, magnitude and risk associated with APIs and other chemicals within the Nairobi/Athi river basin, in Kenya, East Africa. The catchment showed an extensive downstream impact zone estimated to extend 75 km, mostly, but not exclusively, derived from the direct discharge of untreated wastewater from the urban centre of Nairobi city. The exact extent of the downstream boundary of the Nairobi city impact zone was unclear owing to the inputs of untreated wastewater sources from the continuous urbanized areas along the river, which counteracted the natural attenuation caused by dilution and degradation. The most frequently detected APIs and chemicals were caffeine, carbamazepine, trimethoprim, nicotine, and sulfamethoxazole. Paracetamol, caffeine, sulfamethoxazole, and trimethoprim alone contributed 86% of the total amount of APIs determined along the Nairobi/Athi catchment. In addition to direct discharge of untreated domestic wastewater attributed to the informal settlements within the conurbation, other sources were linked to the industrial area in Nairobi City where drug formulation is known to occur, the Dandora landfill and veterinary medicines from upstream agriculture. It was shown that there was a possible environmental risk of API ecotoxicological effects beyond the end of the traditional impact zone defined by elevated biochemical oxygen demand concentrations; with metronidazole and sulfamethoxazole exhibiting the highest risk.

Biochar incorporation increased nitrogen and carbon retention in a waste-derived soil.

The synthesis of manufactured soils converts waste materials to value-added products, alleviating pressures on both waste disposal infrastructure and topsoils. For manufactured soils to be effective media for plant growth, they must retain and store plant-available nutrients, including nitrogen. In this study, biochar applications were tested for their ability to retain nitrogen in a soil manufactured from waste materials. A biochar, produced from horticultural green waste, was added to a manufactured soil at 2, 5 and 10 % (by weight), then maintained at 15 °C and irrigated with water (0.84 mL m-2 d-1) over 6 weeks. Total dissolved nitrogen concentrations in soil leachate decreased by 25.2, 30.6 and 44.0 % at biochar concentrations of 2, 5 and 10 %, respectively. Biochar also changed the proportions of each nitrogen-fraction in collected samples. Three mechanisms for biochar-induced nitrogen retention were possible: i) increased cation and anion exchange capacity of the substrate; ii) retention of molecules within the biochar pore spaces; iii) immobilisation of nitrogen through microbial utilisation of labile carbon further supported by increased soil moisture content, surface area, and pH. Dissolved organic carbon concentrations in leachate were reduced (-34.7 %, -28.9 %, and -16.7 %) in the substrate with 2, 5 and 10 % biochar additions, respectively. Fluorescein diacetate hydrolysis data showed increased microbial metabolic activity with biochar application (14.7 ±â€¯0.5, 25.4 ±â€¯5.3, 27.0 ±â€¯0.1, 46.1 ±â€¯6.1 µg FL g-1 h-1 for applications at 0, 2, 5, and 10 %, respectively), linking biochar addition to enhanced microbial activity. These data highlight the potential for biochar to suppress the long-term turnover of SOM and promote carbon sequestration, and a long-term sustainable growth substrate provided by the reuse of waste materials diverted from landfill.

Impact of the wastewater-mixing zone on attenuation of pharmaceuticals in natural waters: Implications for an impact zone inclusive environmental risk assessment.

The direct discharge of untreated wastewater has been identified as an important source of environmental contamination by active pharmaceutical ingredients and other 'down-the-drain' chemicals in developing countries. It necessitates the development of an environmental risk assessment approach for the resulting impact zone. This study was designed to investigate the impact of low level of dilution (<10) on the natural attenuation processes of distribution and degradation within the impact zone. Dilution of the untreated wastewater resulted in increased desorption and corresponding environmental concentrations. The presence/absence of the microbial population in the batches affected the degree of sorption depending on the compound charge (i.e. positive or negative), highlighting an experimental technical bias. The degradation half-lives of acebutolol and diclofenac increased with increasing dilution and resulted in higher environmental persistence. The modelling of the biochemical oxygen demand (BOD) allowed an estimate of the temporal end boundary of the impact zone to be predicted as 24h. Therefore, it was concluded that most of the investigated compounds would persist beyond the end of the impact zone as defined by the return to environmental BOD concentrations. It is proposed that, within environmental risk assessment protocols, the impact zone should be considered as a semi-natural wastewater treatment area in such a way to allow the estimate of environmental concentrations of pharmaceuticals beyond its end.

Soil sterilisation methods for use in OECD 106: How effective are they?

Under many circumstances chemical risk assessments for pharmaceuticals and other substances are required to differentiate between 'loss' of a chemical from the aqueous phase as a result of abiotic (sorption or precipitation reactions) or biotic (biodegradation) processes. To distinguish only abiotic processes, it is necessary to work under sterile conditions. Reported methods include poisoning the soil with sodium azide, irradiation and autoclaving. However, a key aspect of any testing is the representativeness of the matrix and so any sterilisation procedure needs to ensure that the integrity of the sample is maintained, in particular particle size distribution, pH and organic carbon partitioning potential. A number of controlled laboratory experiments were performed on 3 different types of soil. Results indicated that none of the methods successfully sterilised the soils and some physico-chemical changes in soils were identified post-treatment. Autoclaving destroyed the soil structure, therefore potentially affecting its sorption behaviour and sodium azide changed the pH of the loam soil solution by 0.53 pH units. Gamma irradiation exhibited least disruption to the tested soils physico-chemical properties. It was therefore concluded that gamma irradiation was the best available method for sterilising soils in preparation for sorption-desorption experiments; however care needs to be taken with this method to ensure that microbial activity is absent, or quantified if present. The changes to soils after sterilisation varied depending on the individual soil properties, indicating that soils should be studied on a case-by-case basis.

Sorption of active pharmaceutical ingredients in untreated wastewater effluent and effect of dilution in freshwater: Implications for an "impact zone" environmental risk assessment approach.

Evidence of ecotoxicological effects of active pharmaceuticals ingredients (APIs) has increased research into their environmental fate. In low and low-middle income countries (LLMICs) the main source of APIs to surface waters is from discharge of untreated wastewater. Consequently, concentrations of APIs can be relatively high in the "impact zone" downstream of a discharge point. Little is known about the fate of APIs in these impact zones. In this laboratory scale investigation, the effect of successive dilution of synthetic untreated wastewater (dilution factor 1 to 10) on the distribution of APIs was studied. The sorption was consistent with the chemical properties of each compound: charge, lipophilicity, and structure. Dilution increased desorption of the basic and neutral APIs (up to 27.7%) and correlated with their lipophilicity (R2>0.980); the positive charge was of secondary importance. Anions did not significantly desorb (<10% loss). Increased concentrations of dissolved organic matter at dilutions of 8 and 10 times that of untreated wastewater coincided with lower dissolved API concentrations. The data showed a clear trend in the desorption process of APIs that may lead to higher exposure risk than anticipated. Therefore, it is suggested that these aspects should be accounted for in the development of dedicated environmental risk assessment approach for APIs in riverine impact zones of LLMICs countries.

Antarctic sea ice region as a source of biogenic organic nitrogen in aerosols.

Climate warming affects the development and distribution of sea ice, but at present the evidence of polar ecosystem feedbacks on climate through changes in the atmosphere is sparse. By means of synergistic atmospheric and oceanic measurements in the Southern Ocean near Antarctica, we present evidence that the microbiota of sea ice and sea ice-influenced ocean are a previously unknown significant source of atmospheric organic nitrogen, including low molecular weight alkyl-amines. Given the keystone role of nitrogen compounds in aerosol formation, growth and neutralization, our findings call for greater chemical and source diversity in the modelling efforts linking the marine ecosystem to aerosol-mediated climate effects in the Southern Ocean.

Pharmaceuticals in soils of lower income countries: Physico-chemical fate and risks from wastewater irrigation.

Population growth, increasing affluence, and greater access to medicines have led to an increase in active pharmaceutical ingredients (APIs) entering sewerage networks. In areas with high wastewater reuse, residual quantities of APIs may enter soils via irrigation with treated, partially treated, or untreated wastewater and sludge. Wastewater used for irrigation is currently not included in chemical environmental risk assessments and requires further consideration in areas with high water reuse. This study critically assesses the contemporary understanding of the occurrence and fate of APIs in soils of low and lower-middle income countries (LLMIC) in order to contribute to the development of risk assessments for APIs in LLMIC. The physico-chemical properties of APIs and soils vary greatly globally, impacting on API fate, bioaccumulation and toxicity. The impact of pH, clay and organic matter on the fate of organic ionisable compounds is discussed in detail. This study highlights the occurrence and the partitioning and degradation coefficients for APIs in soil:porewater systems, API usage data in LLMICS and removal rates (where used) within sewage treatment plants as key areas where data are required in order to inform robust environmental risk assessment methodologies.

Bacterio-plankton transformation of diazepam and 2-amino-5-chlorobenzophenone in river waters.

Benzodiazepines are a large class of commonly-prescribed drugs used to treat a variety of clinical disorders. They have been shown to produce ecological effects at environmental concentrations, making understanding their fate in aquatic environments very important. In this study, uptake and biotransformations by riverine bacterio-plankton of the benzodiazepine, diazepam, and 2-amino-5-chlorobenzophenone, ACB (a photo-degradation product of diazepam and several other benzodiazepines), were investigated using batch microcosm incubations. These were conducted using water and bacterio-plankton populations from contrasting river catchments (Tamar and Mersey, UK), both in the presence and absence of a peptide, added as an alternative organic substrate. Incubations lasted 21 days, reflecting the expected water residence time in the catchments. In River Tamar water, 36% of diazepam (p < 0.001) was removed when the peptide was absent. In contrast, there was no removal of diazepam when the peptide was added, although the peptide itself was consumed. For ACB, 61% was removed in the absence of the peptide, and 84% in its presence (p < 0.001 in both cases). In River Mersey water, diazepam removal did not occur in the presence or absence of the peptide, with the latter again consumed, while ACB removal decreased from 44 to 22% with the peptide present. This suggests that bacterio-plankton from the Mersey water degraded the peptide in preference to both diazepam and ACB. Biotransformation products were not detected in any of the samples analysed but a significant increase in ammonium concentration (p < 0.038) was measured in incubations with ACB, confirming mineralization of the amine substituent. Sequential inoculation and incubation of Mersey and Tamar microcosms, for 5 periods of 21 days each, did not produce any evidence of increased ability of the microbial community to remove ACB, suggesting that an indigenous consortium was probably responsible for its metabolism. As ACB degradation was consistent, we propose that the aquatic photo-degradation of diazepam to ACB, followed by mineralization of ACB, is a primary removal pathway for these emerging contaminants. As ACB is photo-produced by several benzodiazepines, this pathway should be relevant for the removal of other benzodiazepines that enter the freshwater environment.

Characterisation and quantification of organic phosphorus and organic nitrogen components in aquatic systems: a review.

This review provides a critical assessment of knowledge regarding the determination of organic phosphorus (OP) and organic nitrogen (ON) in aquatic systems, with an emphasis on biogeochemical considerations and analytical challenges. A general background on organic phosphorus and organic nitrogen precedes a discussion of sample collection, extraction, treatment/conditioning and preconcentration of organic phosphorus/nitrogen from sediments, including suspended particulate matter, and waters, including sediment porewaters. This is followed by sections on the determination of organic phosphorus/nitrogen components. Key techniques covered for organic phosphorus components are molecular spectrometry, atomic spectrometry and enzymatic methods. For nitrogen the focus is on the measurement of total organic nitrogen concentrations by carbon hydrogen nitrogen analysis and high temperature combustion, and organic nitrogen components by gas chromatography, high-performance liquid chromatography, gel electrophoresis, mass spectrometry, nuclear magnetic resonance spectrometry, X-ray techniques and enzymatic methods. Finally future trends and needs are discussed and recommendations made.