Above the law? How motivated moral reasoning shapes evaluations of high performer unethicality.

Recent revelations have brought to light the misconduct of high performers across various fields and occupations who were promoted up the organizational ladder rather than punished for their unethical behavior. Drawing on principles of motivated moral reasoning, we investigate how employee performance biases supervisors' moral judgment of employee unethical behavior and how supervisors' performance-focus shapes how they account for moral judgments in promotion recommendations. We test our model in three studies: a field study of 587 employees and their 124 supervisors at a Fortune 500 telecom company, an experiment with two samples of working adults, and an experiment that directly varied explanatory mechanisms. Evidence revealed a moral double standard such that supervisors rendered less punitive judgment of the unethical acts of higher performing employees. In turn, supervisors' bottom-line mentality (i.e., fixation on achieving results) influenced the degree to which they incorporated their punitive judgments into promotability considerations. By revealing the moral leniency afforded to higher performers and the uneven consequences meted out by supervisors, our results carry implications for behavioral ethics research and for organizations seeking to retain and promote their higher performers while also maintaining ethical standards that are applied fairly across employees. (PsycInfo Database Record (c) 2023 APA, all rights reserved).

Baseline water quality of the Gold Coast Broadwater, southern Moreton Bay (Australia).

This study establishes baseline water quality characteristics for the Gold Coast Broadwater, southern Moreton Bay (Australia) utilising routinely monitored parameters between 2016 and 2021, across 18 sites. Combined site mean concentrations of NOx-N, NH3-N and total nitrogen were 11.4 ± 33.4 µg/L, 12.7 ± 27.2 µg/L, and 169 ± 109 µg/L, respectively, whilst PO4-P and total phosphorous were 7.30 ± 5.10 µg/L and 21.7 ± 14.1 µg/L. Additionally, total suspended solids and turbidity combined site means were 6.6 ± 6.0 mg/L and 3.4 ± 2.9 NTU, respectively. During high rainfall periods nutrient concentrations increased by up to >200-, >150-, 15-, 12- and >12-fold for NOx-N, NH3-N, TN, PO4-P and TP, respectively, compared to quiescent conditions. Furthermore, TSS and NTU values increased by up to 15- and 40-fold during periods of measured rainfall compared to quiescent conditions.

Restoration of benthic macrofauna promotes biogeochemical remediation of hostile sediments; An in situ transplantation experiment in a eutrophic estuarine-hypersaline lagoon system.

Estuarine ecosystems have very high ecological and economic value, and also act as a buffer for coastal oceans by processing nutrient inputs from terrestrial sources. However, ongoing pressures from increased urbanisation and agriculture, overlaid by climate change, has reduced inflows and increased nutrient loads that challenge the health and buffering capacity of these ecosystems. This study aimed to investigate whether restoring the bioturbating activity of Simplisetia aequisetis (Polychaeta: Nereididae) and other macrofauna could improve biogeochemical conditions in 'hostile' (i.e. hypersaline, sulfide-rich) sediments. To achieve this aim, we conducted an in situ experiment in the Coorong estuarine-lagoon ecosystem, translocating hostile hypersaline sediments, devoid of bioturbating macrofauna, to a 'healthy' (lower salinity) location where macrobenthic fauna naturally occur, and manipulating the S. aequisetis density in the sediments. Porewater, solid-phase, and diffusive equilibrium and diffusive gradient in thin-films (DET/DGT) measurements showed that bioturbation by macrobenthic fauna significantly influenced sediment biogeochemistry and remediated hostile conditions in sediment within a short time (four weeks) irrespective of S. aequisetis density. Bioturbation promoted sediment oxygenation, while salinity and the concentrations of total organic carbon and porewater sulfide, ammonium, and phosphate all decreased over time at all sediment depths. This research highlights the importance of macrobenthic communities and their functional traits for improving sediment conditions, promoting resilience to eutrophication, providing a nature-based remediation option, and in general ensuring healthy functioning of estuarine ecosystems.

Loss of benthic macrofauna functional traits correlates with changes in sediment biogeochemistry along an extreme salinity gradient in the Coorong lagoon, Australia.

Estuarine ecosystems are considered hotspots for productivity, biogeochemical cycling and biodiversity, however, their functions and services are threatened by several anthropogenic pressures. We investigated how abundance and diversity of benthic macrofauna, and their functional traits, correlate to sediment biogeochemistry and nutrient concentrations throughout an estuarine-to-hypersaline lagoon. Benthic communities and functional traits were significantly different across the sites analysed, with higher abundance and more traits expressed in the estuarine region. The results revealed that the benthic trait differences correlated with sediment biogeochemistry and nutrient concentrations in the system. The estuarine regions were dominated by high abundance of large burrowing and bioturbating macrofauna, promoting nutrient cycling and organic matter mineralisation, while these organisms were absent in the hypersaline lagoon, favouring accumulation of organic matter and nutrients in the sediment. The results highlight the importance of preserving healthy benthic communities to maintain ecosystem functioning and mitigate the potential impacts of eutrophication in estuarine ecosystems.

From zero to hero and back to zero: The consequences of status inconsistency between the work roles of multiple jobholders.

The surge of opportunities available through the gig economy has increased the sizeable population of people who hold multiple jobs. Many of these multiple jobholders are full-time employees who have adopted side-hustles-income-generating work performed alongside full-time work. A core and ubiquitous feature of both full-time work and side-hustles is status, or membership in a social hierarchy. Although status has traditionally been investigated as an employee's enduring position in the social hierarchy at their full-time job, employees with side-hustles hold two distinct work-related statuses: status in their full-time job and status in their side-hustle. Having two statuses necessarily creates a situation in which employees' status is either consistent or inconsistent across roles. We investigate the implications of status inconsistency between side-hustles and full-time work for employees' stress, well-being, and performance. We assert that status inconsistency between side-hustles and full-time work requires employees to navigate stress-inducing tensions, such as incongruent role expectations and confusion regarding their sense of self. By extension, we propose that status inconsistency between side-hustles and full-time work promotes more role stress than occupying consistently low-status roles. In a four-wave field study of full-time employees with side-hustles, and their supervisors, we use polynomial regression analysis to test our predictions. We find that status inconsistency diminishes performance in full-time work via role stress and emotional exhaustion. Given the burgeoning gig economy and associated changes to how work is organized, our research has important and timely implications for multiple jobholders and their full-time work organizations. (PsycInfo Database Record (c) 2022 APA, all rights reserved).

Motivated to "roll the dice" on trust: The relationships between employees' daily motives, risk propensity, and trust.

Models of trust have focused on the notion that an employee's trust in a coworker is based on that coworker's trustworthiness and the employee's trust propensity-a generalized tendency to believe others are trustworthy. Although these models capture the general assessment of risk associated with trusting a particular coworker, they provide insufficient insight into why an employee might take the risk associated with trust on a particular day. Bringing the concept of risk propensity-the tendency to accept or avoid risk-from the decision-making literature into the trust literature, we build a model of trust that suggests employees' trusting behaviors stem from both their calculated assessment of risk (encapsulated in trustworthiness and trust propensity) and their tendency to take those risks. We draw on motivated reasoning theory (Kunda, 1990) and the decision-making literature to suggest that employees' daily strivings for achievement, affiliation, stimulation, and security induce a biased reasoning process that influences employees' risk propensity that day. Our test of this theoretical model demonstrates that generalized work motives have an indirect effect on employees' trust in their coworkers, through risk propensity, that goes above and beyond established bases of trust. (PsycInfo Database Record (c) 2022 APA, all rights reserved).

Trophic transfer of microbeads to jellyfish and the importance of aging microbeads for microplastic experiments.

Concepts in microplastics studies are not well established due to the emerging nature of microplastic research, especially in jellyfish. We conducted experiments to test whether ephyrae would ingest more microbeads via trophic transfer than direct ingestion and whether medusae would ingest more aged microbeads than virgin microbeads. We exposed ephyrae of Aurelia coerulea to two treatments, aged microbeads and Artemia nauplii that had ingested microbeads. We found that the ephyrae ingested 35 times more microbeads via trophic transfer than by direct ingestion. In the second experiment, medusae of A. coerulea were exposed to virgin microbeads and microbeads in seawater under a 12/12 light/dark cycle or constant darkness. Ingestion rates of microbeads from the light incubation were greater than those from the dark incubation or virgin microbeads, suggesting the likely presence of photosynthetic organisms in biofilms from the light incubation increased the palatability of the microbeads and promoted their ingestion.

Assessment of microplastics in discharged treated wastewater and the utility of Chrysaora pentastoma medusae as bioindicators of microplastics.

Microplastics are ubiquitous pollutants in aquatic environments globally. Wastewater treatment plants are considered to be a major source of microplastics and jellyfish have been proposed as potential bioindicators of microplastic pollution. We tested whether treated wastewater influenced the concentration and/or composition of microplastics in the receiving water by comparing the concentration and composition of microplastics in seawater collected in the wastewater plume and at sites distant from treated wastewater releases in the Gold Coast Broadwater, Australia, and at sites within the nearby Tweed River estuaries, which receives >10 times less wastewater discharge. In addition, tiger sea nettle Chrysaora cf. pentostoma medusae were collected to determine whether more microplastics occurred in the guts of the medusae nearby diffusers and whether the microplastics ingested by medusae were representative of those present in the water column. The concentration and composition of microplastics at the wastewater release sites did not significantly differ from sites that were distant from them. Eighty three percent of medusae contained microplastics in their guts and the composition of the ingested microplastics differed significantly from that in the surrounding water. We concluded that discharged treated wastewater had no detectable effect on levels or composition of microplastics in the receiving water and that C. pentostoma are unsuitable bioindicators because the microplastics they ingested did not represent those available in their environment.

Evaluation of the Chelex-DGT technique for the measurement of rare earth elements in the porewater of estuarine and arine sediments.

This study describes the validation of a diffusive gradients in thin film (DGT) technique for determining lanthanide rare earth elements (REEs) and in situ measurements of REEs in sediment pore waters. Laboratory experiments demonstrated that Chelex-100 binding layers had uptake efficiencies ranging from 78.0% to 92.3% for all REEs. An eluent of 1 mol L-1 HNO3 was optimal with elution efficiencies >80% for all REEs. Mass versus time experiments confirmed that DGT uptake was linear for all REEs at pH 8.1, 6.6 and 3.9 over a period of 3-4 days. Diffusion coefficients (D) for all REEs were derived from these experiments using the slopes of the linear regressions. D values varied with pH but were generally similar to values reported previously. The Chelex-100 DGT technique from this study is highly sensitive for the measurement of REE concentrations with detection limits ranging from 1.8 to 45 ng L-1 based on 72 h deployments allowing measurements of natural trace REE levels. Chelex-100 DGT devices were deployed in estuarine and marine sediments over a period of 72 h and most REE porewater concentrations (50-10,410 ng L-1) were successfully measured. Individual depth profiles of REEs showed a complex response, with many peaks and troughs suggesting a high degree of sediment heterogeneity. Depth-averaged REE concentrations showed a typical zig-zag distribution, although patterns varied between sediment types, after the REEs were normalised using the Queensland Mud Composite shale reference. The Chelex-100 DGT technique therefore shows promise for REE measurements in sediments.

Limited ingestion, rapid egestion and no detectable impacts of microbeads on the moon jellyfish, Aurelia aurita.

Jellyfish are voracious planktonic predators that may be susceptible to ingesting microplastics. We measured rates of ingestion and egestion of microbeads by Aurelia aurita (Scyphozoa) and evaluated whether ingesting microbeads affected metabolism or gut epithelia. Ingestion rates were measured by exposing medusae to microbeads and randomly sampling them 6 times over a 32 h period to determine the number of microbeads in their tissues. Egestion rates were measured by exposing medusae to microbeads for 1 h before transferring them to kreisels without microbeads and sampling them 6 times over 8 h. Respiration rates of medusae were determined using incubations and potential damage to gut epithelia was evaluated using histopathology. Medusae ingested few microbeads and egested them within 8 h. Microbeads had no effect on respiration and the histology. We concluded that the medusae may recognise microbeads as non-food particles and that their ingestion caused undetectable physiological and histological harm.

Hot pursuit: The affective consequences of organization-set versus self-set goals for emotional exhaustion and citizenship behavior.

An unintended side effect of the goal-setting literature's focus on cognitive dynamics has been an insufficient acknowledgment of how employees affectively experience high-performance goals. This is potentially a crucial oversight, considering the substantial body of research that has demonstrated the impact of employees' affective states on organizationally relevant attitudes and behaviors. Drawing on cognitive-motivational-relational theory (Lazarus, 1991), we explore the discrete affective states elicited by high-performance goals. We suggest that a key to understanding these affective states is the source of the performance goal. The literature has largely considered whether goals are organization-set or self-set to be a peripheral aspect of a goal's impact on employees. From an affective perspective, however, an employee's self-set performance goals may be appraised and experienced quite differently than performance goals assigned by the organization. We build a theoretical model that suggests high organization-set goals will elicit anxiety due to an appraisal characterized by uncertainty and threat, whereas high self-set goals will elicit enthusiasm due to an appraisal characterized by positive expectations and benefit. We propose that these affective states will have diverging effects on employees' emotional exhaustion and, subsequently, their extrarole performance. We support our model both in the field via a 4-wave study conducted with police officers and their supervisors and in the laboratory via an experiment in which we manipulated goal source during a performance task. (PsycINFO Database Record (c) 2020 APA, all rights reserved).

Denitrification and benthic metabolism in lowland pit lakes: The role of trophic conditions.

Over recent decades, a great number of pit lakes have been formed, as a result of sand and gravel quarrying in river floodplains that are often also heavily exploited for agriculture. These lakes can act as nutrient filters and regulate the nitrogen pollution resulting from agricultural fertiliser use. In this paper we report the main outcomes of a study of the major nitrogen pathways in five pit lakes of differing trophic status, located along a lowland stretch of the Po river (Northern Italy). Benthic nitrogen fluxes and denitrification rates were determined in the hypolimnion and denitrification and reactive nitrogen assimilation by microphytobenthos in the littoral zone. We tested the hypothesis that lake depth and trophic status can impair denitrification and/or reactive nitrogen assimilation, compromising the function of the lakes as nutrient filters. In the studied lakes, denitrification and reactive nitrogen assimilation by primary producer communities accounted for substantial nitrogen removal rates, which were among the highest reported in the literature. Benthic nitrogen fluxes and denitrification varied between and within lakes, with depth. The littoral zone and surface waters also supported primary production, favouring nitrogen assimilation and temporal retention in the primary producer biomass. In all lakes, denitrification rates decreased from littoral to hypolimnetic sites. Denitrification rates and net nitrogen assimilation also diminished from oligotrophic to eutrophic conditions. To some extent, in eutrophic lakes there was a transfer of primary production from the benthos to the water column and the benthic system became heterotrophic, reducing the capacity for net nitrogen removal. Overall these results highlight that floodplain pit lakes can provide ecosystem services formerly supplied by natural wetlands. An important factor for management is the development of extensive littoral and shallow water zones, which are critical for maximising the nitrogen removal.

A new colorimetric DET technique for determining mm-resolution sulfide porewater distributions and allowing improved interpretation of iron(II) co-distributions.

Measurement of sulfide in pore waters is critical for understanding biogeochemical processes, especially within coastal sediments. Here we report the development of a new colorimetric DET (diffusive equilibration in thin films) technique for determining mm-resolution, two-dimensional sulfide distributions in sediment pore waters. This colorimetric sulfide DET method was based on the standard spectrophotometric methylene blue assay, but modified to allow quantitation of sulfide by computer imaging densitometry. The method detection and effective upper measurement limits of the optimised technique were 3.7 and 1000 µmol L-1, respectively. The optimised sulfide DET method was combined with the colorimetric iron(II) DET method to obtain co-distributions in coastal seagrass (Zostera muelleri) colonised sediment under light and dark conditions. In the dark, seagrass sediments were more reduced than in the light, with large areas being dominated by high porewater sulfide concentrations. These co-distributions were compared with those obtained using the previously described DET-DGT (diffusive gradients in thin films) method for measuring iron(II) and sulfide co-distributions. There was less overlap of iron(II) and sulfide distributions using the sulfide DET as the two DET methods are influenced most by the later hours of deployment, whereas the sulfide-DGT measurement integrates concentrations over the whole deployment period. Overlap was most apparent in very dynamic sediment zones, such as burrow wall sediments.

Comparison of DET, DGT and conventional porewater extractions for determining nutrient profiles and cycling in stream sediments.

Determining inorganic nutrient profiles to support understanding of nitrogen transformations in stream sediments is challenging, due to nitrification and denitrification being confined to particular conditions in potentially heterogeneous sediment influenced by benthic microalgae, rooted aquatic plants and/or diel light cycles. The diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques allow in situ determination of porewater concentration profiles, and distributions for some solutes. In this study, DGT, DET and conventional porewater extraction (sectioning and centrifugation) methods were compared for ammonium and nitrate in stream sediments under light and dark conditions. Two-dimensional distributions of Fe(ii) and PO4-P were also provided to indicate the degree of spatial and temporal heterogeneity in sediment porewater, which can explain the sources and sinks of ammonium at various depths in the sediments. Although the conventional porewater extraction method consistently measured higher NH4-N concentrations than the DGT and DET techniques, the study showed that the DET measurements were the most reliable indicator of porewater NH4-N concentrations, with the DGT data being usefully supplementary. However, a large proportion of the NO3-N concentrations measured by DGT and DET were close to or below the method detection limits. Therefore, further development of these techniques is required to reduce the blanks and detection limits to allow natural low sediment porewater NO3-N concentrations to be accurately monitored using DGT and DET. The study indicated that benthic microalgae had direct and indirect influences on porewater nutrient distributions over light-dark cycles. Overall, DGT and DET techniques can be useful for monitoring porewater nutrient concentrations and profiles and for determining how biological processes drive changes in sediment nutrient concentrations and distributions.

Contrasting effects of bioturbation on metal toxicity of contaminated sediments results in misleading interpretation of the AVS-SEM metal-sulfide paradigm.

In undisturbed, metal-contaminated marine sediments, porewater metal concentrations are generally low due to their associations with strong binding phases such as organic matter, Fe/Mn (oxy)hydroxides and sulfides. Bioturbating fauna can alter redox conditions and, therefore, metal binding, potentially leading to increased metal bioavailability and subsequent toxicity to inhabiting organisms. Here we assessed the impacts of bioturbation (by bivalves and large amphipod species) on sediment biogeochemistry, metal bioaccumulation and toxicity to a smaller amphipod species in a metal contaminated sediment with low and high acid volatile sulfide (AVS) concentrations. Active bioturbation lowered metal toxicity to reproduction in the sediment with low-AVS (from 90% toxic (non-bioturbated) to 50% toxic (bioturbated)). This corresponded with lower dissolved metal concentrations in the overlying water column and lower metal bioaccumulation. Conversely, toxicity increased due to bioturbation in the sediment with high-AVS (40% toxic (non-bioturbated) to 80% toxic (bioturbated)), coinciding with sulfide oxidation, metal release and greater metal bioaccumulation. The results indicate that the AVS-SEM paradigm (commonly used to estimate the risks of adverse effects to benthic organisms in metal-contaminated sediments) may result in incorrect assessment outcomes in cases where bioturbating organisms rework and oxidize the sediment, or for those sediments where AVS has accumulated due to the inability of larger bioturbating benthic organisms to establish populations.

Assisted natural recovery of hypersaline sediments: salinity thresholds for the establishment of a community of bioturbating organisms.

Hypersaline sediments derived from poor land management or the decommissioning of large-scale salt production contribute to the long-term degradation of aquatic environments. Obstacles impeding remediation of these environments include salt crusts restricting benthic recolonisation, hypersalinity-induced toxicity to organisms, and disruption of biogeochemical cycles. Remediation often focuses on engineered solutions, despite sediment-biota interactions often playing a crucial role in improving long-term remediation and restoration of contaminated areas. The presence of extensive bioturbating communities can assist with flushing of excess salt ions, and the reduction of excess nutrients. Here we investigated the tolerance limits that may impede benthic organism recolonisation of hypersaline sediments. Bioassays on dilutions of a hypersaline sediment (∼400 psu (practical salinity units)) and extracted porewaters were used to assess the acute and chronic tolerances of a range of benthic species. Amphipod, copepod and shrimp species were the least tolerant to hypersalinity; bivalve and gastropod species displayed intermediate tolerance; and crab and polychaete species were the most tolerant, i.e. able to endure prolonged exposure in waters at ≥60 psu. Avoidance tests found many species avoid salinities >50 psu. Short-term endurance tests (time to death) indicated thresholds in the 52-70 psu range through tidal cycle exposures of 6 h (semi-diurnal), 12 h (diurnal), 24 h and 48 h (prolonged). Amphipod reproduction and shrimp larvae development bioassays had EC30's of 46 psu and EC50's in the 54-65 psu range, indicating potential to maintain populations at salinities up to 65 psu. These results will assist in designing successful monitored natural recovery strategies for salt ponds that may supplement the initial engineered approaches.

Too many sheep in the flock? Span of control attenuates the influence of ethical leadership.

There has been growing interest in ethical leadership from both scholars and practitioners because of the positive effects that ethical leaders can have on their subordinates. These benefits come not only from ethical leaders acting as moral exemplars, but also from the tendency for ethical leaders to forge high-quality social exchange relationships with subordinates that help to establish expectations for appropriate conduct and ensure accountability through reciprocal obligation. However, the act of developing and maintaining strong social exchange relationships is resource intensive and requires considerable personal investment from ethical leaders. Extending current theory, we propose that wider spans of control attenuate the positive relationship between ethical leadership and leader-member exchange (LMX). Across two organizational samples, we developed and tested a moderated mediation model in which the effects of ethical leadership on performance, organizational citizenship behavior, and reduced production deviance via LMX were weakened by a widened span of control. Results in both studies supported the hypothesized model. Although it may be tempting to increase the number of subordinates assigned to ethical leaders in an effort to maximize their positive impact, the current findings suggest that the benefits of ethical leadership are diminished as span of control widens. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Removing ammonium from water and wastewater using cost-effective adsorbents: A review.

Ammonium is an important nutrient in primary production; however, high ammonium loads can cause eutrophication of natural waterways, contributing to undesirable changes in water quality and ecosystem structure. While ammonium pollution comes from diffuse agricultural sources, making control difficult, industrial or municipal point sources such as wastewater treatment plants also contribute significantly to overall ammonium pollution. These latter sources can be targeted more readily to control ammonium release into water systems. To assist policy makers and researchers in understanding the diversity of treatment options and the best option for their circumstance, this paper produces a comprehensive review of existing treatment options for ammonium removal with a particular focus on those technologies which offer the highest rates of removal and cost-effectiveness. Ion exchange and adsorption material methods are simple to apply, cost-effective, environmentally friendly technologies which are quite efficient at removing ammonium from treated water. The review presents a list of adsorbents from the literature, their adsorption capacities and other parameters needed for ammonium removal. Further, the preparation of adsorbents with high ammonium removal capacities and new adsorbents is discussed in the context of their relative cost, removal efficiencies, and limitations. Efficient, cost-effective, and environmental friendly adsorbents for the removal of ammonium on a large scale for commercial or water treatment plants are provided. In addition, future perspectives on removing ammonium using adsorbents are presented.

Diffusive Gradients in Thin Films Reveals Differences in Antimony and Arsenic Mobility in a Contaminated Wetland Sediment during an Oxic-Anoxic Transition.

Antimony (Sb) and arsenic (As) are priority environmental contaminants that often co-occur at mining-impacted sites. Despite their chemical similarities, Sb mobility in waterlogged sediments is poorly understood in comparison to As, particularly across the sediment-water interface (SWI) where changes can occur at the millimeter scale. Combined diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques provided a high resolution, in situ comparison between Sb, As, and iron (Fe) speciation and mobility across the SWI in contaminated freshwater wetland sediment mesocosms under an oxic-anoxic-oxic transition. The shift to anoxic conditions released Fe(II), As(III), and As(V) from the sediment to the water column, consistent with As release being coupled to the reductive dissolution of iron(III) (hydr)oxides. Conversely, Sb(III) and Sb(V) effluxed to the water column under oxic conditions and fluxed into the sediment under anoxic conditions. Porewater DGT-DET depth profiles showed apparent decoupling between Fe(II) and Sb release, as Sb was primarily mobilized across the SWI under oxic conditions. Solid-phase X-ray absorption spectroscopy (XAS) revealed the presence of an Sb(III)-S phase in the sediment that increased in proportion with depth and the transition from oxic to anoxic conditions. The results of this study showed that Sb mobilization was decoupled from the Fe cycle and was, therefore, more likely linked to sulfur and/or organic carbon (e.g., most likely authigenic antimony sulfide formation or Sb(III) complexation by reduced organic sulfur functional groups).

Comparing in situ colorimetric DET and DGT techniques with ex situ core slicing and centrifugation for measuring ferrous iron and dissolved sulfide in coastal sediment pore waters.

In productive coastal sediments the separation between different biogeochemical zones (e.g. oxic, iron(III)-reducing and sulfate-reducing) may be on the scale of millimetres. Conventional measurement techniques simply cannot resolve changes in pore water solute concentrations over such small distances. The diffusive equilibration in thin films (DET) and the diffusive gradients in thin films (DGT) techniques allow in situ determination of pore water solute concentration profiles with one-dimensional profiles and/or two-dimensional distributions on the millimetre scale. Here we compare measurements of pore water iron(II) and sulfide using conventional core sampling (slicing and centrifugation) and colorimetric DET-DGT techniques. DET-DGT samplers were deployed within replicate sediment cores from three different sites, which were processed by slicing and centrifugation following retrieval of the samplers, so that the measurements were approximately co-located. Iron(II) concentrations were determined by DET at all three sites (0.3-262 µmol L-1), while dissolved sulfide was consistently measured by DGT at one site only (0.003-112 µmol L-1). Pore water concentrations of iron(II) and sulfide determined conventionally following pore water extraction (iron(II); 0.4-88 µmol L-1 and sulfide; 0.05-36 µmol L-1), were systematically lower than the colorimetric DET and DGT measurements in the same sample. This underestimation was most likely due to the mixing of sediment from different biogeochemical zones during pore water extraction, which resulted in the precipitation of iron(II) and sulfide. This study shows that conventional pore water extraction methods can be unreliable for the determination of redox-active solutes due to artefacts associated with pore water mixing.