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The River Itchen and River Test, two chalk streams in Southern England, are sites of special scientific interest. These ecosystems face a number of environmental pressures from anthropogenic inputs of organic pollutants. Hence, we investigated the occurrence of these chemicals within the two catchments. Spot water samples (1 L) were collected at nineteen sites along the catchment on two occasions (March and June 2019). Samples were extracted (HLB-L sorbent disks) and analysed using high-resolution liquid chromatography-quadrupole-time-of-flight mass spectrometry and gas chromatography-mass spectrometry. Compounds were identified against commercially available databases. Using this approach, we found 115 pharmaceutical and personal care products, 81 plant protection products and 35 industrial chemicals. This complex mixture of pollutants covered a range of physico-chemical properties and included priority substances in the EU Water Framework Directive or currently on the third Watch List. Both rivers had similar chemical profiles for both months. Herbicides and fungicides were dominant in the spring, whereas insecticides occurred more frequently in the summer. Point discharges from wastewater treatment plants were the main source of pharmaceutical and personal care products. Agricultural activities were the main contributor to the presence of plant protection products. The impact of these organic chemicals on the ecology, particularly on macroinvertebrate biodiversity, is unknown and warrants further investigation. Our suspect screening approach could guide future toxicological investigations to assess the environmental impacts of these diverse chemicals.

Volatile organic compounds (VOCs) play an important role in urban air pollution, both as primary pollutants and through their contribution to the formation of secondary pollutants, such as tropospheric ozone and secondary organic aerosols. In this study, more than 30 VOC species were continuously monitored in the two most populous cities in Vietnam, namely Ho Chi Minh City (Hien et al., 2019 and March 2019) and Hanoi (March 2019). In parallel with ambient VOC sampling, grab sampling was used to target the most prevalent regional-specific emission sources and estimate their emission factors (EFs). Emission ratios (ERs) obtained from ambient sampling were compared between Vietnamese cities and other cities across the globe. No significant differences were observed between HCMC and Hanoi, suggesting the presence of similar sources. Moreover, a good global agreement was obtained in the spatial comparison within a factor of 2, with greater ER for aromatics and pentanes obtained in the Vietnamese cities. The detailed analysis of sources included the evaluation of EF from passenger cars, buses, trucks, motorcycles, 3-wheeled motorcycles, waste burning, and coal-burning emissions. Our comparisons between ambient and near-source concentration profiles show that road transport sources are the main contributors to VOC concentrations in Vietnamese cities. VOC emissions were calculated from measured EF and consumption data available in Hanoi and compared with those estimated by a global emission inventory (EDGAR v4.3.2). The total VOC emissions from the road transport sector estimated by the inventory do not agree with those calculated from our observations which showed higher total emissions by a factor of 3. Furthermore, the inventory misrepresented the VOCs speciation, mainly for isoprene, monoterpenes, aromatics, and oxygenated compounds. Accounting for these differences in regional air quality models would lead to improved predictions of their impacts and help to prioritise pollution reduction strategies in the region.

Hanoi and Ho Chi Minh City (HCM), the most populous cities in Vietnam, have received increasing global attention because of their poor air pollution status. As part of the recent UK-Vietnam 2-Cities project, the concentrations of trace metals in fine particulate matter have been characterized. 24-hour samples of PM2 were collected at 2 sites in Hanoi and 3 sites in HCM during two 4-week periods in September/October 2018 and March 2019. The soluble fraction of 15 trace metal(oid)s (Fe, Al, Mn, Ti, Zn, V, Cu, Ni, Co, Cd, Pb, Th, Cr, As, and Sb) bound to PM2 were analyzed by ICP-MS. The results show that Zn was the most abundant soluble metal in PM2 in both cities, with very large numbers of road vehicles (e.g. tyre wear) likely contributing in both cities and non-ferrous metal production being a substantial additional source in Hanoi. Fe and Al, derived from crustal sources, were the dominant metals after Zn. Most trace metals concentrations in Hanoi were higher than in HCM, especially toxic metals such as Pb, Cd, Cr and As. V and Ni were the only two metals having higher concentrations in HCM than in Hanoi, likely due to shipping emissions (combustion of heavy fuel oil) that strongly affect the air quality in HCM. Coal-power plants and non-ferrous metal production are likely to be the major sources of trace metals in Hanoi. Health risk assessment shows that a high carcinogenic risk exists for inhalation exposure of soluble trace metals bound to PM2 in both cities.

Isoprene is the most important biogenic volatile organic compound in the atmosphere. Its calculated impact on ozone (O3) is critically dependent on the model isoprene oxidation chemical scheme, in particular the way the isoprene-derived nitrates (IN) are treated. By combining gas chromatography with mass spectrometry, we have developed a system capable of separating, and unambiguously measuring, individual IN isomers. In this paper we report measurements from its first field deployment, which took place in Beijing as part of the Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-Beijing) programme, along with box model simulations using the Master Chemical Mechanism (MCM) (v.3.3.1) to assess the key processes affecting the production and loss of the IN. Seven individual isoprene nitrates were identified and quantified during the summer campaign: two β-isoprene hydroxy nitrates (IHN); four δ isoprene carbonyl nitrates (ICN); and propanone nitrate. Whilst we had previously demonstrated that the system can measure the four δ-IHN, we found no evidence of them in Beijing. The two β-IHN mixing ratios are well correlated with an R2 value of 0.85. The mean for their ratio ((1-OH, 2-ONO2)-IHN : (4-OH, 3-ONO2)-IHN) is 3.4 and exhibits no clear diel cycle (the numbers in the names indicate the carbon (C) atom in the isoprene chain to which the radical is added). Examining this in a box model demonstrates its sensitivity to nitric oxide (NO), with lower NO mixing ratios favouring (1-OH, 2-ONO2)-IHN over (4-OH, 3-ONO2)-IHN. This is largely a reflection of the modelled ratios of their respective precursor peroxy radicals which, at NO mixing ratios of less than 1 part per billion (ppb), increase substantially with decreasing NO. Interestingly, this ratio in the peroxy radicals still exceeds the kinetic ratio (i.e. their initial ratio based on the yields of the adducts from OH addition to isoprene and the rates of reaction of the adducts with oxygen (O2)) even at NO mixing ratios as high as 100 ppb. The relationship of the observed β-IHN ratio with NO is much weaker than modelled, partly due to far fewer data points, but it agrees with the model simulation in so far as there tend to be larger ratios at sub 1 ppb amounts of NO. Of the δ-ICN, the two trans (E) isomers are observed to have the highest mixing ratios and the mean isomer ratio (E-(4-ONO2, 1-CO)-ICN to E-(1-ONO2, 4-CO)-ICN)) is 1.4, which is considerably lower than the expected ratio of 6 for addition of NO3 in the C1 and C4 carbon positions in the isoprene chain. The MCM produces far more δ-ICN than observed, particularly at night and it also simulates an increase in the daytime δ-ICN that greatly exceeds that seen in the observations. Interestingly, the modelled source of δ-ICN is predominantly during the daytime, due to the presence in Beijing of appreciable daytime amounts of NO3 along with isoprene. The modelled ratios of δ-ICN to propanone nitrate are very different to the observed. This study demonstrates the value of speciated IN measurements to test our understanding of the isoprene degradation chemistry. Our interpretation is limited by the uncertainties in our measurements and relatively small data set, but highlights areas of the isoprene chemistry that warrant further study, in particular the NO3 initiated isoprene degradation chemistry.

Pollution of surface water by polar pesticides is a major environmental risk, particularly in river catchments where potable water supplies are abstracted. In these cases, there is a need to understand pesticide sources, occurrence and fate. Hence, we developed a novel strategy to improve water quality management at the catchment scale using passive sampling coupled to suspect screening and multivariate analysis. Chemcatcher® passive sampling devices were deployed (14 days) over a 12 month period at eight sites (including a water supply works abstraction site) in the Western Rother, a river catchment in South East England. Sample extracts (n = 197) were analysed using high-resolution liquid chromatography-quadrupole-time-of-flight mass spectrometry and compounds identified against a commercially available database. A total of 128 pesticides from different classes were found. Statistical analysis of the qualitative screening data was used to identify clusters of pesticides with similar spatiotemporal pollution patterns. This enabled pesticide sources and fate to be identified. At the water supply works abstraction site, spot sampling and passive sampling were found to be complementary, however, the passive sampling method in conjunction with suspect screening detected 50 pesticides missed by spot sampling combined with targeted analysis. Geospatial data describing pesticide application rates was found to be poorly correlated to their detection frequency using the Chemcatcher®. Our analysis prioritised 61 pesticides for inclusion in a future water quality risk assessment at the abstraction site. It was also possible to design a seasonal monitoring programme to effectively characterise the spatiotemporal pesticide profiles within the catchment. A work flow of how to incorporate passive sampling coupled to suspect screening into existing regulatory monitoring is proposed. Our novel approach will enable water quality managers to target the mitigation (non-engineered actions) of pesticide pollution within the catchment and hence, to better inform drinking water treatment processes and save on operational costs.

The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

A novel and rapid approach to characterise the occurrence of contaminants of emerging concern (CECs) in river water is presented using multi-residue targeted analysis and machine learning-assisted in silico suspect screening of passive sampler extracts. Passive samplers (Chemcatcher®) configured with hydrophilic-lipophilic balance (HLB) sorbents were deployed in the Central London region of the tidal River Thames (UK) catchment in winter and summer campaigns in 2018 and 2019. Extracts were analysed by; (a) a rapid 5.5-min direct injection targeted liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for 164 CECs and (b) a full-scan LC coupled to quadrupole time of flight mass spectrometry (QTOF-MS) method using data-independent acquisition over 15 min. From targeted analysis of grab water samples, a total of 33 pharmaceuticals, illicit drugs, drug metabolites, personal care products and pesticides (including several EU Watch-List chemicals) were identified, and mean concentrations determined at 40 ± 37 ng/L-1. For targeted analysis of passive sampler extracts, 65 unique compounds were detected with differences observed between summer and winter campaigns. For suspect screening, 59 additional compounds were shortlisted based on mass spectral database matching, followed by machine learning-assisted retention time prediction. Many of these included additional pharmaceuticals and pesticides, but also new metabolites and industrial chemicals. The novelty in this approach lies in the convenience of using passive samplers together with machine learning-assisted chemical analysis methods for rapid, time-integrated catchment monitoring of CECs.

The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO

Pesticides present at trace concentrations are a common cause of poor water quality. Their concentrations can change dynamically, due to the stochastic nature of pesticide pollution. Consequently, characterisation of pesticide residues that are intermittently present, poses significant monitoring and analytical challenges. Traditional approaches rely on quantitation of a limited number of pesticides present in a discrete water sample. Expanding the analytical suite and/or the frequency of sampling to meet these challenges is often impractical. Comprehensive methods are needed, with selectivity and sensitivity for the hundreds of pesticides potentially present, and temporal representativeness to ensure changing conditions are understood, in order to identify and prioritise risk. Recent analytical advances have enabled the targeted screening of hundreds of compounds in the same run, and automated work-flows can now reliably identify compounds through the comparison of retention time and accurate mass with spectral libraries. Screening generates large qualitative data sets, therefore, there is a need for improved monitoring methods and data interpretation strategies to reduce the need for repetition, and increase the quality of information for end-users. Passive sampling is an in situ time integrative technique, increasingly used for monitoring pesticides in water. Here, we describe a method using the Chemcatcher® passive sampler, coupled to targeted screening using liquid chromatography-quadrupole-time-of-flight mass spectrometry, and a commercially available library. Statistical analysis was performed using Agilent Mass Profiler Professional software. Water sampling took place over one year, at three riverine sites in the south of England, UK. Statistical interpretation of time integrative data from passive sampling could distinguish regular and episodic pesticide inputs, and detected compounds neglected by routine monitoring methods. One hundred and eleven pesticides were identified including legacy and current use compounds with diverse origins and uses. Spatial and temporal trends were identified enabling prioritisation of seasonal monitoring at each site. This approach maximises the utility of qualitative assessment and may help water quality managers to rationalise pesticide fate in future, providing significant additional insight without the need to increase the scope and cost of monitoring.

The aim of this study was to carry out a bioaccessibility-based risk assessment of polycyclic aromatic hydrocarbons (PAHs) in soils from sites of different anthropogenic activities in Lagos, Nigeria. Using an in vitro gastrointestinal model—Fed Organic Estimation Human Simulation Test method (FOREShT), the concentration of bioaccessible 16 priority US Environmental Protection Agency (USEPA) PAHs in soils were determined. Total concentration of 16 priority USEPA PAHs was also determined. The concentration range was 702–253,922 ng g−1 and 92–760 ng g−1 for total and bioaccessible PAHs, respectively. For persons involved with activities at these sites no health risks were observed, based on bioaccessibility values of PAHs. Mean daily intake of PAHs from these soils were below the oral mean daily intake threshold for PAHs in food. Also, overall estimated theoretical cancer risk (2.5 × 10−09, 6.5 × 10−07, 5.5 × 10−10, 2.7 × 10−09, 6.5 × 10−10, 9.5 × 10−10, 2.0 × 10−09, and 4.1 × 10−07 for the eight sites based on their bioaccessible concentration) for exposure to PAHs in surface soils were below the health guidelines for extreme (1 × 10−04) and normal (1 × 10−06) exposures.

Volatile organic compounds (VOCs) and oxygenated VOCs (OVOCs) were measured in Ho Chi Minh City (HCMC) and Hanoi, the two largest and most populous cities in Vietnam. The purpose of this study is to better understand the VOC atmospheric composition and their role in ground-level ozone formation. Online measurements of a wide range of VOCs and other pollutants were conducted using numerous instruments during different seasons (dry and rainy) in HCMC and Hanoi (spring). Our results show that the mean mixing ratio of total measured VOCs in Hanoi was 80.8 ± 40.7 ppb (mean ± standard deviation), and was similar to that observed during the rainy season (75.2 ± 44.8 ppb) in HCMC. During the dry season campaign in HCMC, which was coincident with the Hanoi campaign, total VOC was around 50% lower (40.7 ± 19.5 ppb), largely a result of increased planetary boundary layer (PBL) height and the direction of the prevailing wind. VOC profiles in both cities were dominated by alkanes (31–35%) and OVOCs (27–33%) and the proportion of alkenes (13–17%) and aromatics (12–19%) were comparable. Similarities in diurnal variation for most VOC species (except for isoprene) are seen in both cities with two clear peaks during the morning (7:00–8:00 a.m.) and evening (18:00 p.m.) rush hours, as observed for vehicular-combustion tracers (acetylene and CO). Comparisons of the ambient ratios of paired VOCs, namely i/n-pentane, and toluene/benzene, with those reported in motorcycle exhaust, roadside and gasoline samples indicate that motorcycle-related emission is likely a major contributor to VOC pollution. According to the propylene-equivalent concentration (PE conc.) and maximum incremental reactivity (MIR) methods, alkenes and aromatics were determined to be the main contributors to reactivity and ozone potential formation. Furthermore, the initial mixing ratio of VOC species was estimated based on the photochemical age method. The consumed VOCs (initial VOCs minus measured VOCs) has a similar variation trend to ground-level ozone, and a good correlation is observed in HCMC. In contrast, this result was not seen in Hanoi despite relatively high levels of PE conc. and MIR.

Metaldehyde is a molluscicide and the active ingredient in formulated slug pellets used for the protection of crops. Due to its mobility in the environment it is frequently found in river catchments, often at concentrations exceeding the EU Drinking Water Directive limit of 100 ng L-1 for a single pesticide. This presents a major problem for water companies in the UK where such waters are abstracted for production of potable drinking water supplies. Therefore, it is important to understand the sources, transport and fate of this emerging pollutant of concern in the aquatic environment. We monitored metaldehyde in two contrasting river catchments (River Dee (8 sites) and River Thames (6 sites)) over a twelve month period that coincided with the agricultural application period of the molluscicide. Spot samples of water were collected typically weekly or fortnightly. Chemcatcher® passive samplers were deployed consecutively every two weeks. At the River Dee, there was little variability in the concentrations of metaldehyde (-1) measured in the spot samples of water. The Chemcatcher® gave similar time-weighted average concentrations which were higher following increased rain fall events. At the River Thames, concentrations of metaldehyde varied more widely (-1) with several samples exceeding 100 ng L-1. Generally these concentrations were reflected in the time-weighted average concentrations obtained using the Chemcatcher®. Both monitoring techniques gave complementary data for identifying input sources, and in the development of catchment management plans and environmental remediation strategies.

Chemcatcher® and POCIS passive sampling devices are widely used for monitoring polar organic pollutants in water. Chemcatcher® uses a bound Horizon Atlantic™ HLB-L sorbent disk as receiving phase, whilst the POCIS uses the same material in the form of loose powder. Both devices (n = 3) were deployed for 21 days in the final effluent at three wastewater treatment plants in South Wales, UK. Following deployment, sampler extracts were analysed using liquid chromatography time-of-flight mass spectrometry. Compounds were identified using an in-house database of pharmaceuticals using a metabolomics workflow. Sixty-eight compounds were identified in all samplers. For the POCIS, substantial losses of sorbent (11–51%) were found during deployment and subsequent laboratory analysis, necessitating the use of a recovery factor. Percentage relative standard deviations varied (with 10 compounds exceeding 30% in both samplers) between individual compounds and between samplers deployed at the three sites. The relative performance of the two devices was evaluated using the mass of analyte sequestered, measured as an integrated peak area. The ratio of the uptake of the pharmaceuticals for the POCIS versus Chemcatcher® was lower (1.84x) than would be expected on the basis of the ratio of active sampling areas (3.01x) of the two devices. The lower than predicted uptake may be attributable to the loose sorbent material moving inside the POCIS when deployed in the field in the vertical plane. In order to overcome this, it is recommended to deploy the POCIS horizontally inside the deployment cage. Electronic supplementary material The online version of this article (10.1007/s11356-020-09077-5) contains supplementary material, which is available to authorized users.

Increased concentrations of phosphorus (P) in riverine systems lead to eutrophication and can contribute to other environmental effects. Chalk rivers are known to be particularly sensitive to elevated P levels. We used high-frequency (daily) automatic water sampling at five distinct locations in the upper River Itchen (Hampshire, UK) between May 2016 and June 2017 to identify the main P species (including filterable reactive phosphorus, total filterable phosphorus, total phosphorus and total particulate phosphorus) present and how these varied temporally. Our filterable reactive phosphorus (considered the biologically available fraction) data were compared with the available Environment Agency total reactive phosphorus (TRP) values over the same sampling period. Over the trial, the profiles of the P fractions were complex; the major fraction was total particulate phosphorus with the mean percentage value ranging between 69 and 82% of the total P present. Sources were likely to be attributable to wash off from agricultural activities. At all sites, the FRP and Environment Agency TRP mean concentrations over the study were comparable. However, there were a number of extended time periods (1 to 2 weeks) where the mean FRP concentration (e.g. 0.62 mg L−1) exceeded the existing regulatory values (giving a poor ecological status) for this type of river. Often, these exceedances were missed by the limited regulatory monitoring procedures undertaken by the Environment Agency. There is evidence that these spikes of elevated concentrations of P may have a biological impact on benthic invertebrate (e.g. blue-winged olive mayfly) communities that exist in these ecologically sensitive chalk streams. Further research is required to assess the ecological impact of P and how this might have implications for the development of future environmental regulations. Electronic supplementary material The online version of this article (10.1007/s10661-020-8138-0) contains supplementary material, which is available to authorized users.

We comprehensively review the current state-of-the-art of environmental monitoring for hydrophobic organic contaminants in aqueous matrices using passive sampling devices. Principles of the theory of passive sampling are presented. Strategies for passive sampler design and operation, limitations in performance and data quality-assurance and quality-control are reviewed. Advances in applications of available passive sampling devices are extensively critiqued. Future trends and current challenges facing practitioners and barriers to further adoption of the devices are discussed.

International audience; Groundwater systems are being increasingly used to provide potable and other water supplies. Due to human activities, a range of organic pollutants is often detected in groundwater. One source of groundwater contamination is via stormwater infiltration basins, however, there is little information on the types of compounds present in these collection systems and their influence on the underlying groundwater. We developed an analytical strategy based on the use of passive sampling combined with liquid chromatography/high resolution quadrupole-time-of-flight mass spectrometry for screening for the presence of pesticide and pharmaceutical compounds in groundwater and stormwater runoff. Empore™ disk-based passive samplers (SDB-RPS and SDB-XC sorbents) were exposed, using for the first time a new specially designed deployment rig, for 10 days during a rainfall event in five different stormwater infiltration systems around Lyon, France. Stormwater runoff and groundwater (via a well, upstream and downstream of each basin) was sampled. Exposed Empore™ disks were solvent extracted (acetone and methanol) and the extracts analysed using a specific suspect compound screening workflow. High resolution mass spectrometry coupled with a suspect screening approach was found to be a useful tool as it allows a more comprehensive analysis than with targeted screening whilst being less time consuming than non-targeted screening. Using this analytical approach, 101 suspect compounds were tentatively identified, with 40 of this set being subsequently confirmed. The chemicals detected included fungicides, herbicides, insecticides, indicators of human activity, antibiotics, antiepileptics, antihypertensive and non-steroidal anti-inflammatory drugs as well as their metabolites. Polar pesticides were mainly detected in groundwater and pharmaceuticals were more frequently found in runoff. In terms of detection frequency of the pollutants, groundwater impacted by infiltration was found not to be significantly more contaminated than non-impacted groundwater.

Many rivers in urbanised catchments in South Africa are polluted by raw sewage and effluent to an extent that their ecological function has been severely impaired. The Hennops and Jukskei Rivers lying in the Hartbeespoort Dam catchment are two of the worst impacted rivers in South Africa and are in need of rehabilitation. Passive sampling (Chemcatcher® with a HLB receiving phase) together with high-resolution tandem mass spectrometry–targeted screening was used to provide high sensitivity and selectivity for the identification of a wide range of emerging pollutants in these urban waters. Over 200 compounds, including pesticides, pharmaceuticals and personal care products, drugs of abuse and their metabolites were identified. Many substances (~ 180) being detected for the first time in surface water in South Africa. General medicines and psychotropic drugs were the two most frequently detected groups in the catchment. These accounted for 49% of the emerging pollutants found. Of the general medicines, antihypertensive agents, beta-blocking and cardiac drugs were the most abundant (28%) classes detected. The Hennops site, downstream of a dysfunctional wastewater treatment plant, was the most polluted with 123 substances detected. From the compounds detected, peak intensity–based prioritisation was used to identify the five most abundant pollutants, being in the order caffeine > lopinavir > sulfamethoxazole > cotinine > trimethoprim. This work provides the largest available high-quality dataset of emerging pollutants detected in South African urban waters. The data generated in this study provides a solid foundation for subsequent work to further characterise (suspect screening) and quantify (target analysis) these substances. Electronic supplementary material The online version of this article (10.1007/s10661-019-7515-z) contains supplementary material, which is available to authorized users.

Understanding the sorption of pharmaceuticals to sewage sludge during waste water treatment processes is important for understanding their environmental fate and in risk assessments. The degree of sorption is defined by the sludge/water partition coefficient (Kd). Experimental Kd values (n = 297) for active pharmaceutical ingredients (n = 148) in primary and activated sludge were collected from literature. The compounds were classified by their charge at pH 7.4 (44 uncharged, 60 positively and 28 negatively charged, and 16 zwitterions). Univariate models relating log Kd to log Kow for each charge class showed weak correlations (maximum R2 = 0.51 for positively charged) with no overall correlation for the combined dataset (R2 = 0.04). Weaker correlations were found when relating log Kd to log Dow. Three sets of molecular descriptors (Molecular Operating Environment, VolSurf and ParaSurf) encoding a range of physico-chemical properties were used to derive multivariate models using stepwise regression, partial least squares and Bayesian artificial neural networks (ANN). The best predictive performance was obtained with ANN, with R2 = 0.62–0.69 for these descriptors using the complete dataset. Use of more complex Vsurf and ParaSurf descriptors showed little improvement over Molecular Operating Environment descriptors. The most influential descriptors in the ANN models, identified by automatic relevance determination, highlighted the importance of hydrophobicity, charge and molecular shape effects in these sorbate-sorbent interactions. The heterogeneous nature of the different sewage sludges used to measure Kd limited the predictability of sorption from physico-chemical properties of the pharmaceuticals alone. Standardization of test materials for the measurement of Kd would improve comparability of data from different studies, in the long-term leading to better quality environmental risk assessments., Graphical abstract Image 1, Highlights • Understanding sorption of pharmaceuticals to sludge is important in risk assessment. • Predicting sorption on molecular properties limited by heterogeneous nature of sludge • Models based only on the partition coefficient gave poor predictive models. • Non-linear artificial neural network models improve predictability. • Descriptors that influenced sorbate-sorbent interactions were identified.

Metaldehyde is the active ingredient in most slug pellets used to protect crops. This molluscicide is considered an emerging pollutant and is frequently detected in surface water bodies above the EU statutory drinking water limit of 0.1 μg L−1 for a pesticide. This presents a challenge for providers of drinking water. Understanding the sources, transport and environmental fate of this compound is therefore important. This critical review discusses these aspects including monitoring and analytical techniques used for the detection of metaldehyde in environmental matrices. Novel techniques used for the removal of metaldehyde from drinking water are presented together with potential catchment management strategies and initiatives useful for the mitigation of this molluscicide in the environment.

The presence of polar pesticides in environmental waters is a growing problem. After application their migration into the aqueous phase is promoted by their high water solubility. Transport processes are usually complex and inputs are generally stochastic; this makes monitoring of this class of pesticides challenging using low volume spot samples of water. Recently there has been a trend to use passive samplers to monitor pesticides in river catchments as it is an in-situ time integrative sampling technique. The three main types of device used for this purpose are, Chemcatcher®, POCIS and o-DGT. This article reviews the fate and current state-of-the-art for monitoring polar pesticides in aqueous matrices. Principles and the theory of passive sampling and strategies for passive sampler design and operation are presented. Advances in the application of passive sampling devices for measuring polar pesticides are extensively critiqued; future trends in their use are also discussed.

Metaldehyde is recognised as an emerging contaminant. It is a powerful molluscicide and is the active compound in many types of slug pellets used for the protection of crops. The application of pellets to land generally takes place between August and December when slugs thrive. Due to its high use and physico-chemical properties, metaldehyde can be present in the aquatic environment at concentrations above the EU Drinking Water Directive limit of 100 ng L−1 for a single pesticide. Such high concentrations are problematic when these waters are used in the production of drinking water. Being able to effectively monitor this pollutant of concern is important. We compared four different monitoring techniques (spot and automated bottle sampling, on-line gas chromatography/mass spectrometry (GC/MS) and passive sampling) to estimate the concentration of metaldehyde. Trials were undertaken in the Mimmshall Brook catchment (Hertfordshire, UK) and in a feed in a drinking water treatment plant for differing periods between 17th October and 31st December 2017. This period coincided with the agricultural application of metaldehyde. Overall, there was a good agreement between the concentrations measured by the four techniques, each providing complementary information. The highest resolution data was obtained using the on-line GC/MS. During the study, there was a large exceedance (500 ng L−1) of metaldehyde that entered the treatment plant; but this was not related to rainfall in the area. Each monitoring method had its own advantages and disadvantages for monitoring investigations, particularly in terms of cost and turn-a-round time of data. Electronic supplementary material The online version of this article (10.1007/s10661-019-7221-x) contains supplementary material, which is available to authorized users.

Diet has been established as a major source of exposure to Polycyclic aromatic hydrocarbon for humans (PAHs) especially nonsmokers. Therefore their presence in plants constitute a major health concern. This research aims at determining the concentration and profile of sixteen US-EPA priority PAHs in tropical edible vegetables (Corchorus olitorius (Ewedu), Celosia argentea (Soko), Amaranthus cruentus L (Grain amaranthus/Tete), Telfairia occidentale (Ugwu), Basella alba (Amunu tutu/White Spinash), Lactuca Sativa(Lettuce), Allium ascalonicum (Spring Onions/Alubasa elewe), Talinum Triangulare (Water leaf)), grown on potted contaminated soils. Vegetable grown on potted contaminated soils and contaminated soils were extracted using n-hexane/acetone mixture in ultrasonic bath. Extracts were purified using C18 solid-phase extraction cartridge (5 mL). Resultant extracts were quantified for PAHs on an Agilent 6890 Gas chromatography/mass spectrometer (GC/MS). Total PAH concentration in contaminated soils and plants grown on them were 200 - 250,000 ng g−1 and 100-5,000 ng g−1, respectively. Two and three ringed PAHs which are the less toxic were the dominant PAH type present in most of the plant parts. Telfairia occidentale(Ugwu) consistently grew on all the soils samples which suggest it possess some potential for phyto remediation. Lactuca sativa (Lettuce) had few growth only the least contaminated soils. Its ability to grow on soils with low contamination makes it a potential bio indicators for polluted soils.

Assessment of the fate of pharmaceutical residues in the environment involves the measurement or prediction of their sewage sludge partition coefficient (Kd). Sewage sludge can be classified into four types: primary, activated, secondary and digested, each one with different physical and chemical properties. Published studies have measured Kd for pharmaceuticals in a variety of sludge types. This paper discusses the variability of reported Kd values of pharmaceuticals in different types of sewage sludge, using a dataset generated from the literature. Using a meta-analysis approach, it was shown that the measured Kd values depend on the type of sludge used in the test. Recommendations are given for the type of sludge to be used when studying the partitioning behaviour of pharmaceuticals in waste water treatment plants. Activated sludge is preferred due to its more homogenous nature and the ease of collection of consistent samples at a plant. Weak statistical relationships were found between Kd values for activated and secondary sludge, and for activated and digested sludge. Pooling of Kd values for these sludge types is not recommended for preliminary fate and risk assessments. In contrast, statistical analyses found stronger similarities between Kd values reported for the same pharmaceutical in primary and activated sludges. This allows the pooling of experimental values for these two sludge types to obtain a larger dataset for modelling purposes.

Acidic herbicides are used to control broad-leaved weeds. They are stable, water-soluble, and with low binding to soil are found frequently in surface waters, often at concentrations above the EU Drinking Water Directive limit of 0.10 μg L−1. This presents a problem when such waters are abstracted for potable supplies. Understanding their sources, transport and fate in river catchments is important. We developed a new Chemcatcher® passive sampler, comprising a 3M Empore™ anion-exchange disk overlaid with a polyethersulphone membrane, for monitoring acidic herbicides (2,4-D, dicamba, dichlorprop, fluroxypyr, MCPA, MCPB, mecoprop, tricolpyr). Sampler uptake rates (R s = 0.044–0.113 L day−1) were measured in the laboratory. Two field trials using the Chemcatcher® were undertaken in the River Exe catchment, UK. Time-weighted average (TWA) concentrations of the herbicides obtained using the Chemcatcher® were compared with concentrations measured in spot samples of water. The two techniques gave complimentary monitoring data, with the samplers being able to measure stochastic inputs of MCPA and mecoprop occurring in field trial 1. Chemcatcher® detected a large input of MCPA not found by spot sampling during field trial 2. Devices also detected other pesticides and pharmaceuticals with acidic properties. Information obtained using the Chemcatcher® can be used to develop improved risk assessments and catchment management plans and to assess the effectiveness of any mitigation and remediation strategies.

According to atmospheric chemistry models, isoprene nitrates play an important role in determining the ozone production efficiency of isoprene; however this is very poorly constrained through observations as isoprene nitrates have not been widely measured. Measurements have been severely restricted largely due to a limited ability to measure individual isoprene nitrate isomers. An instrument based on gas chromatography/mass spectrometry (GCMS) and the associated calibration methods are described for the speciated measurements of individual isoprene nitrate isomers. Five of the primary isoprene nitrates which formed in the presence of NOx by reaction of isoprene with the hydroxyl radical (OH) in the Master Chemical Mechanism are identified using known isomers on two column phases and are fully separated on the Rtx-200 column. Three primary isoprene nitrates from the reaction of isoprene with the nitrate radical (NO3) are identified after synthesis from the already identified analogous hydroxy nitrate. A Tenax adsorbent-based trapping system allows the analysis of the majority of the known hydroxy and carbonyl primary isoprene nitrates, although not the (1,2)-IN isomer, under field-like levels of humidity and showed no impact from typical ambient concentrations of NOx and ozone.

Organotins present a toxicological risk to biota in the aquatic environment. Understanding the behaviour of these compounds in sediment is challenging, with sophisticated analytical techniques required for their measurement. We investigated the use of silica-bound sorbents for diffusive gradients in thin-films (DGT) adsorption gels to pre-concentrate five organotins (monobutlytin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT), triphenyltin (TPhT)) found frequently in coastal sediment. C8 sorbent showed optimum performance in uptake and recovery of organotins for pH and ionic strength ranges typical of coastal waters. Recoveries from adsorption gels deployed in filtered sea water were MBT = 123 ± 20%, DBT = 75 ± 12%, TBT = 81 ± 16%, DPhT = 72 ± 30%, TPhT = 58 ± 10% respectively. Devices were used to investigate DGT fluxes and pore water concentrations of organotins in coastal sediment collected from a contaminated site. DGT fluxes measured in sediment cores for the five organotins ranged between 4.3 × 10−8 – 1.6 ×10−5 ng cm2 s−1. The depletion of organotin species within pore waters at the interface with DGT devices was measured over a series of deployment times (2, 7, 14, 21 and 28 days) and provided estimates of the concentration of organotins in pore waters at Langstone Harbour, UK, prior to depletion by the DGT device and information on their spatial heterogeneity. The novel in situ DGT device developed can pre-concentrate organotins from pore waters in coastal sediment core samples and allows their detection at low environmental concentrations using conventional gas chromatographic/mass spectrometric instrumentation. Use of the DGT device overcomes many problems associated with the conventional pore water sampling of organotins. Our preliminary data suggests it has potential in the future to be a useful tool in investigating the environmental fate of these pollutants. The use of the C8 gel will also allow for the simultaneous sequestration of other semi- and non-polar analytes present in the pore water.

Cyclic volatile methylsiloxanes (cVMS) are used in personal care products and are hydrophobic, volatile and persistent. Their environmental water concentrations are low and are difficult to detect using conventional sampling methods. This study shows the potential of passive sampling for cVMS. We used low-density polyethylene (LDPE) samplers and in-field calibration methods for octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5). 13C-D4 and 13C-D5, methyltris(trimethylsiloxy)silane (MT), tetrakis(trimethylsiloxy)silane (TK), and five deuterated polycyclic aromatic hydrocarbons (PAHs) were used as performance reference compounds (PRCs). Samplers were calibrated (7-d) using effluent at a treatment plant, with uptake of cVMS and losses of the PRCs measured at 12 time-points. Concentrations of D4 (53 ng L−1) and D5 (1838 ng L−1) were stable in the effluent. Uptake of D4 and loss of 13C-D4 were isotropic and equilibrium was approached by 7-d. Two estimates of sampler uptake rate (Rs) were 2.1 L d−1 and 2.5 L d−1. The estimated log LDPE/water partition coefficient was 4.4. The uptake of D5 was slower (Rs = 0.32 L d−1) and equilibrium was not reached. Offloading of 13C-D5, MT and TK were slow, and isotropic behaviour was not demonstrated for D5. Offloading of PAHs followed the predicted pattern for LDPE. Uptake of cVMS appeared to be under membrane control, due to low diffusion coefficients in LDPE. Samplers can monitor time-weighted average concentrations of D4 for less than a week, and D5 for longer periods. LDPE samplers allow cVMS to be determined at lower concentrations than by spot sampling methods.

Metaldehyde is a potent molluscicide. It is the active ingredient in most slug pellets used for crop protection. This polar compound is considered an emerging pollutant. Due to its environmental mobility, metaldehyde is frequently detected at impacted riverine sites, often at concentrations above the EU Drinking Water Directive limit of 0.1 µg L−1 for an individual pesticide. This presents a problem when such waters are abstracted for use in the production of potable water supplies, as this chemical is difficult to remove using conventional treatment processes. Understanding the sources, transport and fate of this pollutant in river catchments is therefore important. We developed a new variant of the Chemcatcher® passive sampler for monitoring metaldehyde comprising a Horizon Atlantic™ HLB-L disk as the receiving phase overlaid with a polyethersulphone membrane. The sampler uptake rate (Rs) was measured in semi-static laboratory (Rs = 15.7 mL day−1) and in-field (Rs = 17.8 mL day−1) calibration experiments. Uptake of metaldehyde was linear over a two-week period, with no measurable lag phase. Field trials (five consecutive 14 day periods) using the Chemcatcher® were undertaken in eastern England at three riverine sites (4th September-12th November 2015) known to be impacted by the seasonal agricultural use of metaldehyde. Spot samples of water were collected regularly during the deployments, with concentrations of metaldehyde varying widely (~ 0.03–2.90 µg L−1) and often exceeding the regulatory limit. Time weighted average concentrations obtained using the Chemcatcher® increased over the duration of the trial corresponding to increasing stochastic inputs of metaldehyde into the catchment. Monitoring data obtained from these devices gives complementary information to that obtained by the use of infrequent spot sampling procedures. This information can be used to develop risk assessments and catchment management plans and to assess the effectiveness of any mitigation and remediation strategies.

During the recent SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive data set of all halogen species relevant for the atmospheric budget of total organic bromine was collected in the western Pacific region using the Falcon aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully automated in situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers – coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground-based state-of-the-art GC / MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CH2BrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2σ measurement uncertainties. In contrast to the suggestion that the western Pacific could be a region of strongly increased atmospheric VSLS abundance (Pyle et al., 2011), we found only in the upper troposphere a slightly enhanced amount of total organic bromine from VSLS relative to the levels reported in Montzka and Reimann et al. (2011) for other tropical regions. From the SHIVA observations in the upper troposphere, a budget for total organic bromine, including four halons (H-1301, H-1211, H-1202, H-2402), CH3Br and the VSLS, is derived for the level of zero radiative heating (LZRH), the input region for the tropical tropopause layer (TTL) and thus also for the stratosphere. With the exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka and Reimann et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

Short-lived organic brominated compounds make up a significant part of the organic bromine budget in the atmosphere. Emissions of these compounds are highly variable and there are limited measurements, particularly in the extra-tropical upper troposphere/lower stratosphere and tropical troposphere. Measurements of five very short-lived bromomethanes (VSLB) were made in air samples collected on the CARIBIC project aircraft over three flight routes; Germany to Venezuela/Columbia during 2009–2011, Germany to South Africa during 2010 and 2011 and Germany to Thailand/Kuala Lumpur, Malaysia during 2012 and 2013. In the tropical troposphere, as the most important entrance region to the stratosphere, we observe a total mean organic bromine derived from these compounds across all flights at 10–12 km altitude of 3.4 ± 1.5 ppt. Individual mean tropical tropospheric mixing ratios across all flights were 0.43, 0.74, 0.14, 0.23 and 0.11 ppt for CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CH2BrCl respectively. The highest levels of VSLB-derived bromine (4.20 ± 0.56 ppt) were observed in flights between Bangkok and Kuala Lumpur indicating that the South China Sea is an important source region for these compounds. Across all routes, CHBr3 and CH2Br2 accounted for 34% (4.7–71) and 48% (14–73) respectively of total bromine derived from the analysed VSLB in the tropical mid-upper troposphere totalling 82% (54–89). In samples collected between Germany and Venezuela/Columbia, we find decreasing mean mixing ratios with increasing potential temperature in the extra-tropics. Tropical mean mixing ratios are higher than extra-tropical values between 340–350 K indicating that rapid uplift is important in determining mixing ratios in the lower tropical tropopause layer in the West Atlantic tropics. O3 was used as a tracer for stratospherically influenced air and we detect rapidly decreasing mixing ratios for all VSLB above ∼100 ppb O3 corresponding to the extra-tropical tropopause layer.

The polyunsaturated fatty acids (PUFA) arachidonic acid (AA, n-6) and eicosapentaenoic acid (EPA, n-3) are precursors of eicosanoids and other lipid mediators which have critical roles in inflammation. The mediators formed from the different PUFA have different potencies. We hypothesised that metabolic changes associated with colonic mucosal inflammation would modify the bioavailability of the eicosanoid precursors AA and EPA.Colonic mucosa biopsies were obtained from patients with ulcerative colitis and from matched controls. Inflammation was graded endoscopically and histologically. Esterified and non-esterified fatty acids were determined within the biopsies using gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry, respectively.Biopsy samples were collected from 69 UC patients (54 providing both inflamed and non-inflamed mucosa) and 69 controls. Inflamed mucosa had higher AA (p0.001) and lower EPA (p0.010) contents and a higher AA:EPA ratio (p0.001). Inflamed mucosa also had higher docosapentaenoic acid (DPA) and docosahexaenoic acid (DHA) and lower linoleic acid (LA) and α-linolenic acid (α-LNA) contents (all p0.001), compared to non-inflamed and controls. There were significant correlations between severity of inflammation and contents of AA, DPA and DHA (positive correlations) and of LA, α-LNA and EPA (negative correlations).Higher AA, AA:EPA ratio, DPA and DHA and lower LA, α-LNA and EPA are seen in inflamed mucosa in UC and correlate with severity of inflammation. This suggests an alteration in fatty acid metabolism in the inflamed gut mucosa, which may offer novel targets for intervention and should be considered if nutritional strategies are used.

1. Metabolic acidosis due to accumulation of l-5-oxoproline is a rare, poorly understood, disorder associated with acetaminophen treatment in malnourished patients with chronic morbidity. l-5-Oxoprolinuria signals abnormal functioning of the γ-glutamyl cycle, which recycles and synthesises glutathione. Inhibition of glutathione synthetase (GS) by N-acetyl-p-benzoquinone imine (NAPQI) could contribute to 5-oxoprolinuric acidosis in such patients. We investigated the interaction of NAPQI with GS in vitro. 2. Peptide mapping of co-incubated NAPQI and GS using mass spectrometry demonstrated binding of NAPQI with cysteine-422 of GS, which is known to be essential for GS activity. Computational docking shows that NAPQI is properly positioned for covalent bonding with cysteine-422 via Michael addition and hence supports adduct formation. 3. Co-incubation of 0.77 μM of GS with NAPQI (25–400 μM) decreased enzyme activity by 16–89%. Inhibition correlated strongly with the concentration of NAPQI and was irreversible. 4. NAPQI binds covalently to GS causing irreversible enzyme inhibition in vitro. This is an important novel biochemical observation. It is the first indication that NAPQI may inhibit glutathione synthesis, which is pivotal in NAPQI detoxification. Further studies are required to investigate its biological significance and its role in 5-oxoprolinuric acidosis.

International audience

A report on the meeting organized by The Chromatographic Society and the Separation Science Group, Analytical Division of the Royal Society of Chemistry. Over 60 delegates and commercial exhibitors attended this event, held to celebrate the careers of Robert Flanagan and David Perrett, and acknowledge their extensive contributions in the field of clinical analysis.

Passive sampling is proposed as an alternative to traditional grab- and composite-sampling modes. Investigated here is a novel passive sampler configuration, the Chemcatcher containing an Atlantic HLB disk covered by a 0.2 μm poly(ether sulfone) membrane, for monitoring polar organic micropollutants (personal care products, pharmaceuticals, and illicit drugs) in wastewater effluent. In situ calibration showed linear uptake for the majority of detected micropollutants over 9 days of deployment. Sampling rates (RS) were determined for 59 compounds and were generally in the range of 0.01-0.10 L day(-1). The Chemcatcher was also suitable for collecting chiral micropollutants and maintaining their enantiomeric distribution during deployment. This is essential for their future use in developing more accurate environmental risk assessments at the enantiomeric level. Application of calibration data in a subsequent monitoring study showed that the concentration estimated for 92% of micropollutants was within a factor of 2 of the known concentration. However, their application in a legislative context will require further understanding of the properties and mechanisms controlling micropollutant uptake to improve the accuracy of reported concentrations.

Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate.

Graphical abstract, Tributyltin (TBT) is a legacy pollutant in the aquatic environment, predominantly from its use in anti-foulant paints and is listed as a priority hazardous substance in the European Union’s Water Framework Directive (WFD). Measuring low concentrations of TBT and other organotins (e.g. monobutyltin (MBT), dibutyltin (DBT), diphenyltin (DPhT) and triphenyltin (TPhT)) at sub ng/L concentrations in coastal waters using standard laboratory instrumentation is very challenging. Conventional, low injection volume gas chromatography/mass spectrometry (GC/MS) combined with liquid-liquid extraction typically achieves limits of detection for TBT ∼10 ng L−1. We describe a simple, programmed temperature vaporisation-large injection volume (50 μL), GC/MS selected ion monitoring method for measuring DBT, TBT, DPhT and TPhT in coastal waters at lower concentrations. Quantification of MBT was not possible using these injection volumes but was achieved using a 10 μL injection volume together with a reduced injection speed. This new approach offers: • When using a 50 μL injection, limits of detection = 0.70 ng L−1 and limits of quantification = 2.1 ng L−1 for TBT were achieved in derivatised standards. • Recoveries of TBT and TPhT from coastal water >97%. • Time consuming, off-line sample pre-concentration methods are unnecessary.

We use 2005–2009 satellite observations of formaldehyde (HCHO) columns from the OMI instrument to infer biogenic isoprene emissions at monthly 1 × 1° resolution over the African continent. Our work includes new approaches to remove biomass burning influences using OMI absorbing aerosol optical depth data (to account for transport of fire plumes) and anthropogenic influences using AATSR satellite data for persistent small-flame fires (gas flaring). The resulting biogenic HCHO columns (ΩHCHO) from OMI follow closely the distribution of vegetation patterns in Africa. We infer isoprene emission (EISOP) from the local sensitivity S = ΔΩHCHO / ΔEISOP derived with the GEOS-Chem chemical transport model using two alternate isoprene oxidation mechanisms, and verify the validity of this approach using AMMA aircraft observations over West Africa and a longitudinal transect across central Africa. Displacement error (smearing) is diagnosed by anomalously high values of S and the corresponding data are removed. We find significant sensitivity of S to NOx under low-NOx conditions that we fit to a linear function of tropospheric column NO2. We estimate a 40% error in our inferred isoprene emissions under high-NOx conditions and 40–90% under low-NOx conditions. Our results suggest that isoprene emission from the central African rainforest is much lower than estimated by the state-of-the-science MEGAN inventory.

PurposeThis article aims to review the different devices that are available for the in situ monitoring of analytes found in the marine environment.Design/methodology/approachFollowing a short introduction to the topic, this paper discusses physical‐ and chemical‐based sensors, automatic analysers (flow injection, spectroscopic and spectrometric), electrochemical devices and biosensors.FindingsA wide range of in situ monitoring systems (and associated deployment apparatus) for measuring concentrations of various analytes (e.g. nutrients, organic chemicals and metallic elements) have been developed in recent decades. Many of these systems are still at the laboratory or prototype stage and are yet to be fully developed into commercially available products. The harsh conditions often found in the marine environment can further limit the utility and application of these sensors. Further development work is needed; however, the need now is for field deployments, validation and inter‐calibration between sensors and other analytical measurement techniques.Originality/valueThis paper provides up‐to‐date information on in situ technologies that are available, either at the laboratory and prototype stages or commercially, and are suitable for deployment in the marine environment. Applications of these sensing systems are discussed together with their associated advantages and disadvantages over other existing water monitoring methods.

We present results from the OP3 campaign in Sabah during 2008 that allow us to study the impact of local emission changes over Borneo on atmospheric composition at the regional and wider scale. OP3 constituent data provide an important constraint on model performance. Treatment of boundary layer processes is highlighted as an important area of model uncertainty. Model studies of land-use change confirm earlier work, indicating that further changes to intensive oil palm agriculture in South East Asia, and the tropics in general, could have important impacts on air quality, with the biggest factor being the concomitant changes in NO x emissions. With the model scenarios used here, local increases in ozone of around 50 per cent could occur. We also report measurements of short-lived brominated compounds around Sabah suggesting that oceanic (and, especially, coastal) emission sources dominate locally. The concentration of bromine in short-lived halocarbons measured at the surface during OP3 amounted to about 7 ppt, setting an upper limit on the amount of these species that can reach the lower stratosphere.

Measurements of a suite of individual NOy components were carried out at Halley station in coastal Antarctica as part of the CHABLIS campaign (Chemistry of the Antarctic Boundary Layer and the Interface with Snow). Conincident measurements cover over half a year, from austral winter 2004 through to austral summer 2005. Results show clear dominance of organic NOy compounds (PAN and MeONO2) during the winter months, with low concentrations of inorganic NOy. During summer, concentrations of inorganic NOy compounds are considerably greater, while those of organic compounds, although lower than in winter, are nonetheless significant. The relative concentrations of the alkyl nitrates, as well as their seasonality, are consistent with an oceanic source. Multi-seasonal measurements of surface snow nitrate correlate strongly with inorganic NOy species (especially HNO3) rather than organic. One case study in August suggested that, on that occasion, particulate nitrate was the dominant source of nitrate to the snowpack, but this was not the consistent picture throughout the measurement period. An analysis of NOx production rates showed that emissions of NOx from the snowpack overwhelmingly dominate over gas-phase sources. This result suggests that, for certain periods in the past, the flux of NOx into the Antarctic boundary layer can be calculated from ice core nitrate data.