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Patients with posttraumatic stress disorder (PTSD) exhibit smaller regional brain volumes in commonly reported regions including the amygdala and hippocampus, regions associated with fear and memory processing. In the current study, we have conducted a voxel-based morphometry (VBM) meta-analysis using whole-brain statistical maps with neuroimaging data from the ENIGMA-PGC PTSD working group.
Methods
T1-weighted structural neuroimaging scans from 36 cohorts (PTSD n = 1309; controls n = 2198) were processed using a standardized VBM pipeline (ENIGMA-VBM tool). We meta-analyzed the resulting statistical maps for voxel-wise differences in gray matter (GM) and white matter (WM) volumes between PTSD patients and controls, performed subgroup analyses considering the trauma exposure of the controls, and examined associations between regional brain volumes and clinical variables including PTSD (CAPS-4/5, PCL-5) and depression severity (BDI-II, PHQ-9).
Results
PTSD patients exhibited smaller GM volumes across the frontal and temporal lobes, and cerebellum, with the most significant effect in the left cerebellum (Hedges’ g = 0.22, pcorrected = .001), and smaller cerebellar WM volume (peak Hedges’ g = 0.14, pcorrected = .008). We observed similar regional differences when comparing patients to trauma-exposed controls, suggesting these structural abnormalities may be specific to PTSD. Regression analyses revealed PTSD severity was negatively associated with GM volumes within the cerebellum (pcorrected = .003), while depression severity was negatively associated with GM volumes within the cerebellum and superior frontal gyrus in patients (pcorrected = .001).
Conclusions
PTSD patients exhibited widespread, regional differences in brain volumes where greater regional deficits appeared to reflect more severe symptoms. Our findings add to the growing literature implicating the cerebellum in PTSD psychopathology.
Background: Attitudes toward aging influence many health outcomes, yet their relationship with cognition and Alzheimer’s disease (AD) remains unknown. To better understand their impact on cognition and AD risk, we examined whether positive attitudes predict better cognition and diminished risk on AD biomarkers. Methods: A subsample of older adults with a family history of AD (n=54; women=39) from the McGill PREVENT-AD cohort participated in this study. Participants completed the Attitudes to Ageing Questionnaire (AAQ-24), providing three scores: psychosocial loss, psychological growth and physical change. Participants underwent cognitive testing (Rey Auditory Verbal Learning Test, RAVLT; Delis-Kaplan Executive Function System-Color Word Interference Test, D-KEFS-CWIT), and AD blood-based biomarker assessments (p-tau217, Aβ42/40). Regression models tested associations, adjusting for covariates (age, sex, education, depression, APOE4), and were Bonferroni corrected. Results: Positive attitudes were associated with better recall and recognition (RAVLT) and improved word reading, colour naming, switching, and inhibition (D-KEFS-CWIT) (p<0.00077), while negative attitudes showed the opposite pattern. Negative attitudes were correlated with lower Aβ42/40 ratios, while positive attitudes were linked to lower p-tau217 (p<0.0167). Conclusions: These findings demonstrate that positive attitudes predict better cognition and a lower risk profile for AD biomarkers, suggesting that life outlook may be an early disease feature or a risk factor.
Recent changes to US research funding are having far-reaching consequences that imperil the integrity of science and the provision of care to vulnerable populations. Resisting these changes, the BJPsych Portfolio reaffirms its commitment to publishing mental science and advancing psychiatric knowledge that improves the mental health of one and all.
Posttraumatic stress disorder (PTSD) has been associated with advanced epigenetic age cross-sectionally, but the association between these variables over time is unclear. This study conducted meta-analyses to test whether new-onset PTSD diagnosis and changes in PTSD symptom severity over time were associated with changes in two metrics of epigenetic aging over two time points.
Methods
We conducted meta-analyses of the association between change in PTSD diagnosis and symptom severity and change in epigenetic age acceleration/deceleration (age-adjusted DNA methylation age residuals as per the Horvath and GrimAge metrics) using data from 7 military and civilian cohorts participating in the Psychiatric Genomics Consortium PTSD Epigenetics Workgroup (total N = 1,367).
Results
Meta-analysis revealed that the interaction between Time 1 (T1) Horvath age residuals and new-onset PTSD over time was significantly associated with Horvath age residuals at T2 (meta β = 0.16, meta p = 0.02, p-adj = 0.03). The interaction between T1 Horvath age residuals and changes in PTSD symptom severity over time was significantly related to Horvath age residuals at T2 (meta β = 0.24, meta p = 0.05). No associations were observed for GrimAge residuals.
Conclusions
Results indicated that individuals who developed new-onset PTSD or showed increased PTSD symptom severity over time evidenced greater epigenetic age acceleration at follow-up than would be expected based on baseline age acceleration. This suggests that PTSD may accelerate biological aging over time and highlights the need for intervention studies to determine if PTSD treatment has a beneficial effect on the aging methylome.
Functional cognitive disorder is an increasingly recognised subtype of functional neurological disorder for which treatment options are currently limited. We have developed a brief online group acceptance and commitment therapy (ACT)-based intervention.
Aims
To assess the feasibility of conducting a randomised controlled trial of this intervention versus treatment as usual (TAU).
Method
The study was a parallel-group, single-blind randomised controlled trial, with participants recruited from cognitive neurology, neuropsychiatry and memory clinics in London. Participants were randomised into two groups: ACT + TAU or TAU alone. Feasibility was assessed on the basis of recruitment and retention rates, the acceptability of the intervention, and signal of efficacy on the primary outcome measure (Acceptance and Action Questionnaire II (AAQ-II)) score, although the study was not powered to demonstrate this statistically. Outcome measures were collected at baseline and at 2, 4 and 6 months post-intervention, including assessments of quality of life, memory, anxiety, depression and healthcare use.
Results
We randomised 44 participants, with a participation rate of 51.1% (95% CI 40.8–61.5%); 36% of referred participants declined involvement, but retention was high, with 81.8% of ACT participants attending at least four sessions, and 64.3% of ACT participants reported being ‘satisfied’ or ‘very satisfied’ compared with 0% in the TAU group. Psychological flexibility as measured using the AAQ-II showed a trend towards modest improvement in the ACT group at 6 months. Other measures (quality of life, mood, memory satisfaction) also demonstrated small to modest positive trends.
Conclusions
It has proven feasible to conduct a randomised controlled trial of ACT versus TAU.
Commercial targeted sprayer systems allow producers to reduce herbicide inputs but risks the possibility of not treating emerging weeds. Currently, targeted applications with the John Deere system have five spray sensitivity settings, and no published literature discusses the effects of these settings on detecting and spraying weeds of varying species, sizes, and positions in crops. Research was conducted in Arkansas, Illinois, Indiana, Mississippi, and North Carolina on plantings of corn, cotton, and soybean to determine how various factors might influence the ability of targeted applications to treat weeds. These data included 21 weed species aggregated to six classes with height, width, and densities ranging from 25 to 0.25 cm, 25 to 0.25 cm, and 14.3 to 0.04 plants m−2, respectively. Crop and weed density did not influence the likelihood of treating the weeds. As expected, the sensitivity setting alters the ability to treat weeds. Targeted applications (across sensitivity settings, median weed height and width, and density of 2.4 plants m−2) resulted in a treatment success of 99.6% to 84.4% for Convolvulaceae, 99.1% to 68.8% for decumbent broadleaf weeds, 98.9% to 62.9% for Malvaceae, 99.1% to 70.3% for Poaceae, 98.0% to 48.3% for Amaranthaceae, and 98.5% to 55.8% for yellow nutsedge. Reducing the sensitivity setting reduced the ability to treat weeds. The size of weeds aided targeted application success, with larger weeds being more readily treated through easier detection. Based on these findings, various conditions can affect the outcome of targeted multinozzle applications. Additionally, the analyses highlight some of the parameters to consider when using these technologies.
Since cannabis was legalized in Canada in 2018, its use among older adults has increased. Although cannabis may exacerbate cognitive impairment, there are few studies on its use among older adults being evaluated for cognitive disorders.
Methods:
We analyzed data from 238 patients who attended a cognitive clinic between 2019 and 2023 and provided data on cannabis use. Health professionals collected information using a standardized case report form.
Results:
Cannabis use was reported by 23 out of 238 patients (9.7%): 12 took cannabis for recreation, 8 for medicinal purposes and 3 for both purposes. Compared to non-users, cannabis users were younger (mean ± SD 62.0 ± 7.5 vs 68.9 ± 9.5 years; p = 0.001), more likely to have a mood disorder (p < 0.05) and be current or former cigarette smokers (p < 0.05). There were no significant differences in sex, race or education. The proportion with dementia compared with pre-dementia cognitive states did not differ significantly in users compared with non-users. Cognitive test scores were similar in users compared with non-users (Montreal Cognitive Assessment: 20.4 ± 5.0 vs 20.7 ± 4.5, p = 0.81; Folstein Mini-Mental Status Exam: 24.5 ± 5.1 vs 26.0 ± 3.6, p = 0.25). The prevalence of insomnia, obstructive sleep apnea, anxiety disorders, alcohol use or psychotic disorders did not differ significantly.
Conclusion:
The prevalence of cannabis use among patients with cognitive concerns in this study was similar to the general Canadian population aged 65 and older. Further research is necessary to investigate patients’ motivations for use and explore the relationship between cannabis use and mood disorders and cognitive decline.
Residual herbicides are primarily degraded in the soil through microbial breakdown. Any practices that result in increased soil biological activity, such as cover cropping (between cash crop seasons), could lead to a reduced persistence of herbicides in the soil. Furthermore, cover crops can also interfere with herbicide fate by interception. Field trials were conducted between 2020 and 2023 in a corn (Zea mays L.)–soybean [Glycine max (L.) Merr.] rotation to investigate the influence of cover crop (cereal rye [Secale cereale L.] and crimson clover [Trifolium incarnatum L.]) use on soil enzyme activities (β-glucosidase [BG] and dehydrogenase [DHA]), its effect on the concentration of residual herbicides (sulfentrazone, S-metolachlor, cloransulam-methyl, atrazine, and mesotrione) in the soil, and the interception of herbicides by cover crop residue. The use of cover crops occasionally resulted in increased BG and DHA activities relative to the fallow treatment. However, even when there was an increase in the activity of these two enzymes, increased degradation of the residual herbicides was not observed. The initial concentrations of all residual herbicides in the soil were significantly reduced due to interception by cereal rye biomass. Nevertheless, significant reductions in early-season weed biomass were observed when residual herbicides were included in the tank mixture applied at cover crop termination relative to the application of glyphosate plus glufosinate. Results from this research suggest that the use of cereal rye or crimson clover as cover crops (between cash crop seasons) do not impact the persistence of residual herbicides in the soil or reduce their efficacy in controlling weeds early in the growing season.
Partial remission after major depressive disorder (MDD) is common and a robust predictor of relapse. However, it remains unclear to which extent preventive psychological interventions reduce depressive symptomatology and relapse risk after partial remission. We aimed to identify variables predicting relapse and to determine whether, and for whom, psychological interventions are effective in preventing relapse, reducing (residual) depressive symptoms, and increasing quality of life among individuals in partial remission. This preregistered (CRD42023463468) systematic review and individual participant data meta-analysis (IPD-MA) pooled data from 16 randomized controlled trials (n = 705 partial remitters) comparing psychological interventions to control conditions, using 1- and 2-stage IPD-MA. Among partial remitters, baseline clinician-rated depressive symptoms (p = .005) and prior episodes (p = .012) predicted relapse. Psychological interventions were associated with reduced relapse risk over 12 months (hazard ratio [HR] = 0.60, 95% confidence interval [CI] 0.43–0.84), and significantly lowered posttreatment depressive symptoms (Hedges’ g = 0.29, 95% CI 0.04–0.54), with sustained effects at 60 weeks (Hedges’ g = 0.33, 95% CI 0.06–0.59), compared to nonpsychological interventions. However, interventions did not significantly improve quality of life at 60 weeks (Hedges’ g = 0.26, 95% CI -0.06 to 0.58). No moderators of relapse prevention efficacy were found. Men, older individuals, and those with higher baseline symptom severity experienced greater reductions in symptomatology at 60 weeks. Psychological interventions for individuals with partially remitted depression reduce relapse risk and residual symptomatology, with efficacy generalizing across patient characteristics and treatment types. This suggests that psychological interventions are a recommended treatment option for this patient population.
Hand, foot and mouth disease (HFMD) is a contagious communicable disease, with a high incidence in children aged under 10 years. It is a mainly self-limiting disease but can also cause serious neurological or cardiopulmonary complications in some cases, which can lead to death. Little is known about the burden of HMFD on primary care health care services in the UK. The aim of this work was to describe trends in general practitioner (GP) consultations for HFMD in England from January 2017 to December 2022 using a syndromic surveillance network of GPs. Daily GP consultations for HFMD in England were extracted from 1 January 2017 to 31 December 2022. Mean weekly consultation rates per 100,000 population and 95% confidence intervals (CI) were calculated. Consultation rates and rate ratios (RR) were calculated by age group and sex. During the study period, the mean weekly consultation rate for HFMD (per 100,000 registered GP patients) was 1.53 (range of 0.27 to 2.47). In England, children aged 1–4 years old accounted for the largest affected population followed by children <1 years old. We observed a seasonal pattern of HFMD incidence during the non-COVID years, with a seasonal peak of mean weekly rates between months of September and December. HFMD is typically diagnosed clinically rather than through laboratory sampling. Therefore, the ability to look at the daily HFMD consultation rates provides an excellent epidemiological overview on disease trends. The use of a novel GP-in-hours surveillance system allowed a unique epidemiological insight into the recent trends of general practitioner consultations for HFMD. We demonstrate a male predominance of cases, the impact of the non-pharmaceutical interventions during the COVID-19 pandemic, and a change in the week in which the peak number of cases happens post-pandemic.
Novel management strategies for controlling smutgrass have potential to influence sward dynamics in bahiagrass forage systems. This experiment evaluated population shifts in bahiagrass forage following implementation of integrated herbicide and fertilizer management plans for controlling smutgrass. Herbicide treatments included indaziflam applied PRE, hexazinone applied POST, a combination of PRE + POST herbicides, and a nonsprayed control. Fertilizer treatments included nitrogen, nitrogen + potassium, and an unfertilized control. The POST treatment reduced smutgrass coverage regardless of PRE or fertilizer application by the end of the first season and remained low for the 3-yr duration of the experiment (P < 0.01). All treatments, including nontreated controls, reduced smutgrass coverage during year 3 (P < 0.05), indicating that routine harvesting to remove the biomass reduced smutgrass coverage. Bahiagrass cover increased at the end of year 1 with POST treatment (P < 0.01), but only the POST + fertilizer treatment maintained greater bahiagrass coverage than the nontreated control by the end of year 3 (P < 0.05). Expenses associated with the POST + fertilizer treatment totaled US$348 ha−1 across the 3-yr experiment. Other smutgrass control options could include complete removal of biomass (hay production) and pasture renovation, which can cost 3-fold or greater more than POST + fertilizer treatment. Complete removal of biomass may reduce smutgrass coverage by removing mature seedheads, but at a much greater expense of US$2,835 to US$5,825 ha−1, depending on herbicide and fertilizer inputs. Bahiagrass renovation is US$826 ha−1 in establishment costs alone. When pasture production expenses are included for two seasons postrenovation, the total increases to US$1,120 ha−1 across three seasons. The importance of hexazinone and fertilizer as components of smutgrass control in bahiagrass forage was confirmed in this study. Future research should focus on the biology of smutgrass and the role of a PRE treatment in a long-term, larger-scale forage system.
In Michigan, the COVID-19 pandemic severely impacted Black and Latinx communities. These communities experienced higher rates of exposure, hospitalizations, and deaths compared to Whites. We examine the impact of the pandemic and reasons for the higher burden on communities of color from the perspectives of Black and Latinx community members across four Michigan counties and discuss recommendations to better prepare for future public health emergencies.
Methods:
Using a community-based participatory research approach, we conducted semi-structured interviews (n = 40) with Black and Latinx individuals across the four counties. Interviews focused on knowledge related to the pandemic, the impact of the pandemic on their lives, sources of information, attitudes toward vaccination and participation in vaccine trials, and perspectives on the pandemic’s higher impact on communities of color.
Results:
Participants reported overwhelming effects of the pandemic in terms of worsened physical and mental health, financial difficulties, and lifestyle changes. They also reported some unexpected positive effects. They expressed awareness of the disproportionate burden among Black and Latinx populations and attributed this to a wide range of disparities in Social Determinants of Health. These included racism and systemic inequities, lack of access to information and language support, cultural practices, medical mistrust, and varied individual responses to the pandemic.
Conclusion:
Examining perspectives and experiences of those most impacted by the pandemic is essential for preparing for and effectively responding to public health emergencies in the future. Public health messaging and crisis response strategies must acknowledge the concerns and cultural needs of underrepresented populations.
In response to the COVID-19 pandemic, we rapidly implemented a plasma coordination center, within two months, to support transfusion for two outpatient randomized controlled trials. The center design was based on an investigational drug services model and a Food and Drug Administration-compliant database to manage blood product inventory and trial safety.
Methods:
A core investigational team adapted a cloud-based platform to randomize patient assignments and track inventory distribution of control plasma and high-titer COVID-19 convalescent plasma of different blood groups from 29 donor collection centers directly to blood banks serving 26 transfusion sites.
Results:
We performed 1,351 transfusions in 16 months. The transparency of the digital inventory at each site was critical to facilitate qualification, randomization, and overnight shipments of blood group-compatible plasma for transfusions into trial participants. While inventory challenges were heightened with COVID-19 convalescent plasma, the cloud-based system, and the flexible approach of the plasma coordination center staff across the blood bank network enabled decentralized procurement and distribution of investigational products to maintain inventory thresholds and overcome local supply chain restraints at the sites.
Conclusion:
The rapid creation of a plasma coordination center for outpatient transfusions is infrequent in the academic setting. Distributing more than 3,100 plasma units to blood banks charged with managing investigational inventory across the U.S. in a decentralized manner posed operational and regulatory challenges while providing opportunities for the plasma coordination center to contribute to research of global importance. This program can serve as a template in subsequent public health emergencies.
Cross-sectional studies have identified health risks associated with epigenetic aging. However, it is unclear whether these risks make epigenetic clocks ‘tick faster’ (i.e. accelerate biological aging). The current study examines concurrent and lagged within-person changes of a variety of health risks associated with epigenetic aging.
Methods
Individuals from the Great Smoky Mountains Study were followed from age 9 to 35 years. DNA methylation profiles were assessed from blood, at multiple timepoints (i.e. waves) for each individual. Health risks were psychiatric, lifestyle, and adversity factors. Concurrent (N = 539 individuals; 1029 assessments) and lagged (N = 380 individuals; 760 assessments) analyses were used to determine the link between health risks and epigenetic aging.
Results
Concurrent models showed that BMI (r = 0.15, PFDR < 0.01) was significantly correlated to epigenetic aging at the subject-level but not wave-level. Lagged models demonstrated that depressive symptoms (b = 1.67 months per symptom, PFDR = 0.02) in adolescence accelerated epigenetic aging in adulthood, also when models were fully adjusted for BMI, smoking, and cannabis and alcohol use.
Conclusions
Within-persons, changes in health risks were unaccompanied by concurrent changes in epigenetic aging, suggesting that it is unlikely for risks to immediately ‘accelerate’ epigenetic aging. However, time lagged analyses indicated that depressive symptoms in childhood/adolescence predicted epigenetic aging in adulthood. Together, findings suggest that age-related biological embedding of depressive symptoms is not instant but provides prognostic opportunities. Repeated measurements and longer follow-up times are needed to examine stable and dynamic contributions of childhood experiences to epigenetic aging across the lifespan.
Jellyfishes have ecological and societal value, but our understanding of taxonomic identity of many jellyfish species remains limited. Here, an approach integrating morphological and molecular (16S ribosomal RNA and cytochrome oxidase I) data enables taxonomic assessment of the blubber jellyfish found in the Philippines. In this study, we aimed to resolve doubt on the taxonomy of Acromitoides purpurus, a valid binomen at the time of our research. Our morphological findings confirm that this jellyfish belongs to the genus Catostylus, and is distinct from known species of the genus inhabiting the Western Pacific, such as Catostylus ouwensi, Catostylus townsendi, and Catostylus mosaicus. Detailed morphological and molecular analyses of the type specimens from the Philippines with the other Catostylus species revive the binomen Catostylus purpurus and invalidate A. purpurus. Genetic analysis also distinguishes this Philippine jellyfish from C. townsendi and C. mosaicus. Through this study, we arranged several Catostylidae taxa into species inquirendae (Catostylus tripterus, Catostylus turgescens, and Acromitoides stiphropterus) and one genus inquirenda (Acromitoides) and provided an identification key for species of Catostylus. This comprehensive study confirms the blubber jellyfish as C. purpurus, enriching our understanding of jellyfish biodiversity. The integration of morphological and genetic analyses proves vital in resolving taxonomic ambiguities within the Catostylidae family and in the accurate identification of scyphozoan jellyfishes.
Major depressive disorder (MDD) is the leading cause of disability globally, with moderate heritability and well-established socio-environmental risk factors. Genetic studies have been mostly restricted to European settings, with polygenic scores (PGS) demonstrating low portability across diverse global populations.
Methods
This study examines genetic architecture, polygenic prediction, and socio-environmental correlates of MDD in a family-based sample of 10 032 individuals from Nepal with array genotyping data. We used genome-based restricted maximum likelihood to estimate heritability, applied S-LDXR to estimate the cross-ancestry genetic correlation between Nepalese and European samples, and modeled PGS trained on a GWAS meta-analysis of European and East Asian ancestry samples.
Results
We estimated the narrow-sense heritability of lifetime MDD in Nepal to be 0.26 (95% CI 0.18–0.34, p = 8.5 × 10−6). Our analysis was underpowered to estimate the cross-ancestry genetic correlation (rg = 0.26, 95% CI −0.29 to 0.81). MDD risk was associated with higher age (beta = 0.071, 95% CI 0.06–0.08), female sex (beta = 0.160, 95% CI 0.15–0.17), and childhood exposure to potentially traumatic events (beta = 0.050, 95% CI 0.03–0.07), while neither the depression PGS (beta = 0.004, 95% CI −0.004 to 0.01) or its interaction with childhood trauma (beta = 0.007, 95% CI −0.01 to 0.03) were strongly associated with MDD.
Conclusions
Estimates of lifetime MDD heritability in this Nepalese sample were similar to previous European ancestry samples, but PGS trained on European data did not predict MDD in this sample. This may be due to differences in ancestry-linked causal variants, differences in depression phenotyping between the training and target data, or setting-specific environmental factors that modulate genetic effects. Additional research among under-represented global populations will ensure equitable translation of genomic findings.
The authors report on ancient DNA data from two human skeletons buried within the chancel of the 1608–1616 church at the North American colonial settlement of Jamestown, Virginia. Available archaeological, osteological and documentary evidence suggest that these individuals are Sir Ferdinando Wenman and Captain William West, kinsmen of the colony's first Governor, Thomas West, Third Baron De La Warr. Genomic analyses of the skeletons identify unexpected maternal relatedness as both carried the mitochondrial haplogroup H10e. In this unusual case, aDNA prompted further historical research that led to the discovery of illegitimacy in the West family, an aspect of identity omitted, likely intentionally, from genealogical records.
Sperlingite, (H2O)K(Mn2+Fe3+)(Al2Ti)(PO4)4[O(OH)][(H2O)9(OH)]⋅4H2O, is a new monoclinic member of the paulkerrite group, from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria, Germany. It was found in corrosion pits of altered zwieselite, in association with columbite, hopeite, leucophosphite, mitridatite, scholzite, orange–brown zincoberaunite sprays and tiny green crystals of zincolibethenite. Sperlingite forms colourless prisms with pyramidal terminations, which are predominantly only 5 to 20 μm in size, rarely to 60 μm and frequently are multiply intergrown and are overgrown with smaller crystals. The crystals are flattened on {010} and slightly elongated along [100] with forms {010}, {001} and {111}. Twinning occurs by rotation about c. The calculated density is 2.40 g⋅cm–3. Optically, sperlingite crystals are biaxial (+), α = 1.600(est), β = 1.615(5), γ = 1.635(5) (white light) and 2V (calc.) = 82.7°. The optical orientation is X = b, Y = c and Z = a. Neither dispersion nor pleochroism were observed. The empirical formula from electron microprobe analyses and structure refinement is A1[(H2O)0.96K0.04]Σ1.00A2(K0.52□0.48)Σ1.00M1(Mn2+0.60Mg0.33Zn0.29Fe3+0.77)Σ1.99M2+M3(Al1.05Ti4+1.33Fe3+0.62)Σ3.00(PO4)4X[F0.19(OH)0.94O0.87]Σ2.00[(H2O)9.23(OH)0.77]Σ10.00⋅3.96H2O. Sperlingite has monoclinic symmetry with space group P21/c and unit-cell parameters a = 10.428(2) Å, b = 20.281(4) Å, c = 12.223(2) Å, β = 90.10(3)°, V = 2585.0(8) Å3 and Z = 4. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.058 for 5608 reflections with I > 3σ(I). Sperlingite is the first paulkerrite-group mineral to have co-dominant divalent and trivalent cations at the M1 sites; All other reported members have Mn2+ or Mg dominant at M1. Local charge balance for Fe3+ at M1 is achieved by H2O → OH– at H2O coordinated to M1.
A series of synthetic goethites containing varying amounts of Si and P dopants were characterized by X-ray powder diffraction, electron diffraction, microbeam electron diffraction, and Mössbauer spectroscopy. Very low level incorporation produced materials having structural and spectral properties similar to those of poorly crystalline synthetic or natural goethite. At higher incorporation levels, mixtures of noncrystalline materials were obtained which exhibited Mössbauer spectra typical of noncrystalline materials mixed with a superparamagnetic component. Microbeam electron diffraction indicated that these mixtures contained poorly crystalline goethite, poorly crystalline ferrihydrite, and a noncrystalline component. If the material was prepared with no aging of the alkaline Fe3+ solution before the addition of Na2HPO4 or Na2SiO3, materials were obtained containing little if any superparamagnetic component. If the alkaline Fe3+ solution was aged for 48 hr before the addition, goethite nuclei formed and apparently promoted the precipitation of a superparamagnetic phase. The Mössbauer-effect hyperfme parameters and the saturation internal-hyperfine field obtained at 4.2 K were typical of those of goethite; however, the Mössbauer spectra indicated that the ordering temperature, as reflected in the relaxation rate and/or the blocking temperature, decreased with increasing incorporation of Si and P. The complete loss of crystallinity indicates that Si and P did not substitute for Fe, but rather adsorbed on crystal-growth sites, thereby preventing uniform crystal growth.